TWI698333B - Manufacturing method of laminate - Google Patents

Manufacturing method of laminate Download PDF

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Publication number
TWI698333B
TWI698333B TW108128671A TW108128671A TWI698333B TW I698333 B TWI698333 B TW I698333B TW 108128671 A TW108128671 A TW 108128671A TW 108128671 A TW108128671 A TW 108128671A TW I698333 B TWI698333 B TW I698333B
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Taiwan
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adhesive sheet
adhesive
adherend
polymer
weight
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TW108128671A
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Chinese (zh)
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TW201940333A (en
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設樂浩司
野呂弘司
仲野武史
林圭治
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日商日東電工股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
    • B32B43/006—Delaminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H37/00—Article or web delivery apparatus incorporating devices for performing specified auxiliary operations
    • B65H37/04—Article or web delivery apparatus incorporating devices for performing specified auxiliary operations for securing together articles or webs, e.g. by adhesive, stitching or stapling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H41/00—Machines for separating superposed webs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
    • C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/04—Polysulfides
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    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
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    • C09J7/35—Heat-activated
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Folding Of Thin Sheet-Like Materials, Special Discharging Devices, And Others (AREA)

Abstract

本發明提供一種製造積層體之方法，該積層體包含被黏著體與局部地覆蓋該被黏著體之黏著片，且上述黏著片對上述被黏著體之黏著力為5 N/25 mm以上。該積層體製造方法依序包括：貼附步驟，其係於上述被黏著體貼附黏著片材；切割步驟，其係對上述黏著片材中構成上述黏著片之第一區域與不構成上述黏著片之第二區域之邊界實施切斷加工；及局部去除步驟，其係使上述第一區域殘留於上述被黏著體上並且將上述第二區域自上述被黏著體剝離去除。此處，上述局部去除步驟係於上述黏著片材對上述被黏著體之黏著力超過2 N/25 mm之前進行。The present invention provides a method for manufacturing a laminated body, the laminated body includes an adherend and an adhesive sheet partially covering the adherend, and the adhesive force of the adhesive sheet to the adherend is 5 N/25 mm or more. The manufacturing method of the laminated body sequentially includes: an attaching step, which is attached to the adhered body, and an adhesive sheet; a cutting step, of the adhesive sheet forming the first area of the adhesive sheet and not forming the adhesive sheet The boundary of the second area is cut and processed; and a partial removal step is to leave the first area on the adherend and peel off the second area from the adherend. Here, the above partial removal step is performed before the adhesion of the adhesive sheet to the adherend exceeds 2 N/25 mm.

Description

積層體之製造方法Manufacturing method of laminated body

本發明係關於一種積層體之製造方法。 本申請案係主張基於2017年12月28日提出申請之日本專利申請案2017-253311及2018年12月6日提出申請之日本專利申請案2018-228925之優先權，將該等申請案之全部內容作為參照組入至本說明書中。The present invention relates to a method of manufacturing a laminate. This application claims priority based on the Japanese patent application 2017-253311 filed on December 28, 2017 and the Japanese patent application 2018-228925 filed on December 6, 2018, all of these applications The content is incorporated into this manual as a reference.

根據藉由在被黏著體貼附一片或兩片以上之黏著片而利用上述黏著片局部地覆蓋該被黏著體的積層體，可對應於上述黏著劑之外形或配置而表現各種圖案。作為高精度地製造如上所述被黏著體經黏著片局部地覆蓋之積層體之方法，例如一般使用如下方法：如電路基板之保護膜貼合，將黏著片材預先切割成所需之黏著片之形狀，將該黏著片與被黏著體進行位置對準而貼附。作為與此種技術相關之技術文獻，可列舉專利文獻1。 [先前技術文獻] [專利文獻]According to a laminate in which one or two or more adhesive sheets are attached to the adherend and the adherend is partially covered with the adhesive sheet, various patterns can be expressed corresponding to the shape or arrangement of the adhesive. As a method of manufacturing a laminated body in which the adhered body is partially covered by the adhesive sheet with high precision, for example, the following method is generally used: such as laminating the protective film of the circuit board, and cutting the adhesive sheet into the required adhesive sheet in advance The shape of the adhesive sheet and the adherend are aligned and attached. As a technical document related to this technique, Patent Document 1 can be cited. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利申請公開2013-38379號公報[Patent Document 1] Japanese Patent Application Publication No. 2013-38379

[發明所欲解決之問題][The problem to be solved by the invention]

然而，於上述方法中，由於預先將黏著片材切割成所需之黏著片之形狀，繼而進行位置對準而貼合於特定之被黏著體部位，故而產生切割精度與貼合精度兩者之誤差。因此，於今後之小型化、高精細化之電子零件之製造中，有為了良率良好地製造製品而需要價格非常高之設備之虞。又，例如於所切割之黏著片之尺寸較大之情形或形狀複雜之情形等時，有將該黏著片位置精度及形狀精度良好地貼附於被黏著體變得更加困難之虞。尤其，於為了製造耐久性較高之積層體而使用強黏著性之黏著片之情形時，有將該黏著片準確地貼附於被黏著體之操作之難度變高之傾向。However, in the above method, since the adhesive sheet is cut into the desired shape of the adhesive sheet in advance, and then the position is aligned to be attached to the specific adherend part, the cutting accuracy and the lamination accuracy are both produced. error. Therefore, in the future manufacturing of miniaturized and high-definition electronic components, there is a risk that very expensive equipment will be required in order to manufacture products with good yield. In addition, for example, when the size of the cut adhesive sheet is large or the shape is complicated, it may become more difficult to stick the adhesive sheet to the adherend with good position accuracy and shape accuracy. In particular, when a strong adhesive sheet is used in order to produce a laminated body with high durability, the difficulty of the operation of accurately attaching the sheet to the adherend tends to increase.

因此，本發明之目的在於提供一種高效率地製造於被黏著體上精度良好地形成有黏著片之圖案，且該黏著片牢固地接合於被黏著體之積層體的方法。相關之其他發明提供一種適於實施該製造方法之裝置。 [解決問題之技術手段]Therefore, the object of the present invention is to provide a method for efficiently manufacturing the pattern of the adhesive sheet formed on the adherend with high accuracy, and the adhesive sheet is firmly bonded to the laminated body of the adherend. Related other inventions provide a device suitable for implementing the manufacturing method. [Technical means to solve the problem]

藉由本說明書，提供一種積層體之製造方法，該積層體包含被黏著體與局部地覆蓋該被黏著體之黏著片，且上述黏著片對上述被黏著體之黏著力為5 N/25 mm以上。該積層體製造方法依序包括：貼附步驟，其係將包含基材層與積層於該基材層之至少上述被黏著體側之面之黏著劑層的黏著片材貼附於上述被黏著體；切割步驟，其係對上述黏著片材中構成上述黏著片之第一區域與不構成上述黏著片之第二區域之邊界實施切斷加工；及局部去除步驟，其係使上述第一區域殘留於上述被黏著體上並且將上述第二區域自上述被黏著體剝離去除。此處，上述局部去除步驟係於上述黏著片材對上述被黏著體之黏著力超過2 N/25 mm之前進行。According to this specification, a method for manufacturing a laminated body is provided. The laminated body includes an adherend and an adhesive sheet partially covering the adherend, and the adhesive force of the adhesive sheet to the adherend is 5 N/25 mm or more . The manufacturing method of the laminated body sequentially includes: an attaching step of attaching an adhesive sheet comprising a substrate layer and an adhesive layer laminated on at least the surface of the substrate layer on the side of the adherend to the adherend Body; cutting step, which is to cut the boundary between the first area constituting the adhesive sheet and the second area not constituting the adhesive sheet in the adhesive sheet; and a partial removal step, which makes the first area It remains on the adherend and the second area is peeled and removed from the adherend. Here, the above partial removal step is performed before the adhesion of the adhesive sheet to the adherend exceeds 2 N/25 mm.

根據上述製造方法，藉由依序實施上述貼附步驟、上述切割步驟及上述局部去除步驟，可高效率地獲得於被黏著體上形狀精度及位置精度良好地配置有第一區域之構成。又，由於在上述黏著片材對上述被黏著體之黏著力超過2 N/25 mm之前進行上述局部去除步驟，故而容易進行將第二區域自被黏著體剝離之操作，亦不易產生被黏著體之變形或損傷。According to the above manufacturing method, by sequentially performing the attaching step, the cutting step, and the partial removal step, it is possible to efficiently obtain a configuration in which the first region is arranged on the adherend with good shape accuracy and position accuracy. In addition, since the partial removal step is performed before the adhesive force of the adhesive sheet to the adherend exceeds 2 N/25 mm, the operation of peeling the second area from the adherend is easy, and the adherend is not easily generated. The deformation or damage.

於若干種態樣中，作為上述黏著片材，可良好地使用在貼合於聚醯亞胺後於23℃下經過24小時後之黏著力為2 N/25 mm以下者。根據此種黏著片材，可靈活地應對積層體之製造步驟之準備時間。In some aspects, as the above-mentioned adhesive sheet, one can be used well after being attached to polyimide and having an adhesive force of 2 N/25 mm or less after 24 hours at 23°C. According to this adhesive sheet, it is possible to flexibly cope with the preparation time of the manufacturing step of the laminate.

於此處所揭示之積層體製造方法之若干種態樣中，於上述局部去除步驟後進行加熱處理而使上述第一區域對上述被黏著體之黏著力為5 N/25 mm以上。該態樣例如可使用具備如下黏著劑層之黏著片材實施，該黏著劑層含有玻璃轉移溫度未達0℃之聚合物A、及作為具有聚有機矽氧烷骨架之單體與(甲基)丙烯酸系單體之共聚物的聚合物B，但並不限定於此。In some aspects of the laminated body manufacturing method disclosed herein, heat treatment is performed after the partial removal step so that the adhesion of the first region to the adherend is 5 N/25 mm or more. This aspect can be implemented using, for example, an adhesive sheet with an adhesive layer containing polymer A with a glass transition temperature of less than 0°C, and a monomer having a polyorganosiloxane skeleton and (methyl) ) Polymer B which is a copolymer of acrylic monomers, but is not limited to this.

於若干種態樣中，構成上述聚合物A之單體成分可含有N-乙烯基環狀醯胺。使用如上所述含有N-乙烯基環狀醯胺作為構成單體成分之組成之聚合物A的黏著片材由於可發揮良好之黏著力上升性，故而可良好地用於此處所揭示之製造方法之實施。In several aspects, the monomer component constituting the above-mentioned polymer A may contain N-vinyl cyclic amide. The adhesive sheet using the polymer A of the composition containing N-vinyl cyclic amide as the constituent monomer component as described above can be used for the manufacturing method disclosed here because it can exhibit good adhesive force rise. The implementation.

於此處所揭示之積層體製造方法之其他若干種態樣中，於上述局部去除步驟後進行紫外線照射處理而使上述第一區域對上述被黏著體之黏著力為5 N/25 mm以上。該態樣例如可使用具備如下黏著劑層之黏著片材實施，但並不限定於此，該黏著劑層包含含有基礎聚合物與光硬化劑之光硬化性組合物，上述光硬化劑為多官能(甲基)丙烯酸酯，且上述光硬化劑之含量相對於上述基礎聚合物100重量份為1重量份以上且50重量份以下。In several other aspects of the laminated body manufacturing method disclosed herein, ultraviolet radiation treatment is performed after the partial removal step so that the adhesion of the first region to the adherend is 5 N/25 mm or more. This aspect can be implemented using, for example, an adhesive sheet having an adhesive layer, but it is not limited to this. The adhesive layer includes a photocurable composition containing a base polymer and a light curing agent. Functional (meth)acrylate, and the content of the light hardener is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the base polymer.

又，此處所揭示之積層體製造方法亦可以如下態樣實施，即，於上述局部去除步驟後，於常溫下進行保管直至上述第一區域對上述被黏著體之黏著力成為5 N/25 mm以上。 再者，本說明書中，所謂常溫，於未特別說明之情形時，意指約0℃～35℃、典型而言10℃～35℃之溫度。In addition, the manufacturing method of the laminated body disclosed here can also be implemented in the following manner, that is, after the partial removal step, it is stored at room temperature until the adhesion of the first area to the adherend becomes 5 N/25 mm the above. In addition, in this specification, the term "normal temperature" means a temperature of about 0°C to 35°C, typically 10°C to 35°C unless otherwise specified.

於若干種態樣中，作為上述黏著片材，可良好地使用厚度為30 μm以上，且上述基材層之厚度Ts為上述黏著劑層之厚度Ta之2倍以上者。藉由使用此種黏著片材，可獲得容易進行對被黏著體之貼附操作或第二區域之剝離操作的優點。In some aspects, as the adhesive sheet, a thickness of 30 μm or more can be used well, and the thickness Ts of the substrate layer is more than twice the thickness Ta of the adhesive layer. By using such an adhesive sheet, the advantage of easy attachment operation to the adherend or peeling operation of the second area can be obtained.

上述第二區域較佳為以其至少一端到達上述黏著片材之端之方式設定。藉此，可獲得於進行上述局部去除步驟時容易進行第二區域之拾取之優點。就提高拾取性之觀點而言，上述第二區域亦可為到達上述黏著片材之端之一端朝向該黏著片材之端變寬之形狀。The second area is preferably set in such a way that at least one end thereof reaches the end of the adhesive sheet. Thereby, it is possible to obtain the advantage that the second region can be easily picked up during the partial removal step. From the viewpoint of improving the pick-up property, the second region may also have a shape in which an end reaching the end of the adhesive sheet widens toward the end of the adhesive sheet.

此處所揭示之製造方法可以如下態樣良好地實施，即，將面積為2500 cm2 以上且短邊之長度為50 cm以上之黏著片材用於上述貼附步驟。於使用如上所述面積較大且寬度較寬之黏著片材之態樣中，可更有效地發揮藉由採用此處所揭示之製造方法所產生之優點。The manufacturing method disclosed here can be implemented well in such a manner that an adhesive sheet having an area of 2500 cm 2 or more and a short side length of 50 cm or more is used in the above attaching step. In the case of using the adhesive sheet with a larger area and a wider width as described above, the advantages produced by using the manufacturing method disclosed herein can be more effectively utilized.

此處所揭示之製造方法亦可為，作為上述貼附步驟所使用之上述黏著片材及上述被黏著體，使用包含複數個與上述積層體對應之單元者；作為於上述貼附步驟之後進行之步驟，進而包括將上述黏著片材及上述被黏著體分割成上述單元之分割步驟。藉由如此將包含複數個單元之黏著片材貼附於被黏著體後進行分割，可高效率地製造複數個積層體。再者，上述複數個單元之構成可相同亦可不同。The manufacturing method disclosed here may also be that the adhesive sheet and the adherend used in the attaching step include a plurality of units corresponding to the laminated body; as the method performed after the attaching step The step further includes a dividing step of dividing the adhesive sheet and the adherend into the units. By attaching the adhesive sheet including a plurality of units to the adherend and dividing it, a plurality of laminates can be manufactured efficiently. Furthermore, the structures of the above-mentioned plural units may be the same or different.

根據本說明書，提供一種用以製造包含被黏著體及局部地積層於該被黏著體之黏著片之積層體的裝置。該裝置包含貼附黏著片材之貼附機構。又，上述裝置可包含對上述黏著片材實施切斷加工之切割機構。又，上述裝置可包含將上述第二區域剝離之剝離機構。使用具有此種構成之製造裝置，可良好地實施此處所揭示之任一積層體製造方法。According to this specification, an apparatus for manufacturing a laminated body including an adherend and an adhesive sheet partially laminated on the adherend is provided. The device includes an attaching mechanism for attaching an adhesive sheet. In addition, the above-mentioned apparatus may include a cutting mechanism that performs cutting processing on the above-mentioned adhesive sheet. In addition, the device may include a peeling mechanism that peels off the second area. Using the manufacturing apparatus with such a structure, any laminated body manufacturing method disclosed here can be implemented well.

再者，將上述各要素適當組合者亦可包含於藉由本件專利申請案要求專利保護之發明之範圍。Furthermore, the appropriate combination of the above elements can also be included in the scope of the invention claimed by this patent application.

以下，對本發明之較佳之實施形態進行說明。關於本說明書中特別言及之事項以外且實施本發明所需要之事項，業者可基於本說明書所記載之關於發明之實施之指示與申請時之技術常識而理解。本發明可基於本說明書所揭示之內容與該領域之技術常識而實施。 再者，於以下之圖式中，有對發揮相同作用之構件、部位標註相同符號進行說明之情況，有省略或簡化重複之說明之情況。又，圖式所記載之實施形態係為了清楚地說明本發明而模式化，未必準確地表示出實際之尺寸或比例尺。Hereinafter, a preferred embodiment of the present invention will be described. Regarding matters other than those specifically mentioned in this specification and required to implement the present invention, the industry can understand based on the instructions on the implementation of the invention described in this specification and common technical knowledge at the time of application. The present invention can be implemented based on the content disclosed in this specification and common technical knowledge in the field. Furthermore, in the following drawings, members and parts that perform the same function may be described with the same symbols, and repeated descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are modeled in order to clearly explain the present invention, and may not accurately represent actual dimensions or scales.

＜＜積層體之製造方法＞＞ 圖1係表示一實施形態之積層體製造方法之流程圖，圖2係表示藉由該方法所製造之積層體之立體圖，圖3係其III-III線之剖視圖。如圖2、3所示，藉由本實施形態所製造之積層體1包含被黏著體10及局部地覆蓋該被黏著體10之表面10A之黏著片21A、21B。黏著片21A、21B係藉由在將黏著片材20貼附於被黏著體10後，使該黏著片材20中之第一區域21殘留於被黏著體10上且將第二區域22自被黏著體10剝離去除，而由殘留於被黏著體10上之第一區域21所形成。黏著片材20具有於基材層202之單面積層有黏著劑層204之構成。＜＜Method of manufacturing laminated body＞＞ Fig. 1 is a flow chart showing a method of manufacturing a laminated body according to an embodiment, Fig. 2 is a perspective view of a laminated body manufactured by this method, and Fig. 3 is a cross-sectional view taken along the line III-III. As shown in FIGS. 2 and 3, the laminated body 1 manufactured by the present embodiment includes an adherend 10 and adhesive sheets 21A and 21B partially covering the surface 10A of the adherend 10. The adhesive sheets 21A, 21B are made by attaching the adhesive sheet 20 to the adherend 10, so that the first area 21 of the adhesive sheet 20 remains on the adherend 10 and the second area 22 is self-covered The adhesive body 10 is peeled and removed, and is formed by the first area 21 remaining on the adherend 10. The adhesive sheet 20 has a structure in which an adhesive layer 204 is layered on a single area of the base layer 202.

如圖1所示，本實施形態之積層體製造方法依序包括貼附步驟S10、切割步驟S20及局部去除步驟S30。 貼附步驟S10中，將黏著片材20貼附於被黏著體10。該步驟中所使用之黏著片材20包含：作為黏著片21A、21B含有於積層體1之構成要素中之區域即第一區域21、及不成為積層體1之構成要素且僅在積層體1之製造過程中使用之第二區域22。圖2所示之例中，於黏著片材20之寬度之大致中央設定有自該黏著片材20之長度方向之一端呈直線狀延伸至另一端的第二區域22。於貼附步驟S10所使用之黏著片材20中，第一區域21與第二區域22物理性地相連，可將該等區域21、22作為連續之黏著片材20對待。As shown in FIG. 1, the manufacturing method of the laminated body of this embodiment sequentially includes the attaching step S10, the cutting step S20, and the partial removal step S30. In the attaching step S10, the adhesive sheet 20 is attached to the adherend 10. The adhesive sheet 20 used in this step includes the first region 21 that is the area contained in the constituent elements of the laminate 1 as the adhesive sheets 21A, 21B, and the first area 21 that does not become the constituent element of the laminate 1 and is only present in the laminate 1. The second area 22 used in the manufacturing process. In the example shown in FIG. 2, a second region 22 extending linearly from one end of the adhesive sheet 20 in the longitudinal direction to the other end is set in the approximate center of the width of the adhesive sheet 20. In the adhesive sheet 20 used in the attaching step S10, the first area 21 and the second area 22 are physically connected, and these areas 21 and 22 can be treated as a continuous adhesive sheet 20.

切割步驟S20中，對貼附於被黏著體10之黏著片材20之第一區域21與第二區域22之邊界實施切斷加工。例如，如圖4所示，進行沿構成第一區域21與第二區域22之邊界之切斷預定線C照射雷射光L之雷射切斷。再者，圖4表示雷射切斷之例，但切斷加工之方法並無特別限定，可視目的或用途自公知之各種切斷方法中適當選擇。作為此種切斷方法之例，可列舉：CO2 雷射或YAG(Yttrium Aluminium Garnet，釔鋁石榴石)雷射等使用雷射光之雷射切斷；利用湯姆森刀、尖刀、旋轉刀、切刀(knife)等刀具之切斷；刀片(blade)切斷等，但並不限定於該等。切斷方法可單獨使用一種或組合兩種以上使用。In the cutting step S20, the boundary between the first area 21 and the second area 22 of the adhesive sheet 20 attached to the adherend 10 is cut. For example, as shown in FIG. 4, laser cutting is performed in which laser light L is irradiated along the planned cutting line C that constitutes the boundary between the first region 21 and the second region 22. Furthermore, FIG. 4 shows an example of laser cutting, but the method of cutting processing is not particularly limited, and can be appropriately selected from various known cutting methods depending on the purpose or application. Examples of such cutting methods include: CO 2 laser or YAG (Yttrium Aluminium Garnet, Yttrium Aluminium Garnet) laser cutting using laser light; using Thomson knife, sharp knife, rotary knife, Cutting of knives such as a knife; cutting of a blade, but not limited to these. The cutting method can be used alone or in combination of two or more.

局部去除步驟S30係於在貼附步驟中貼附於被黏著體之黏著片材對上述被黏著體之黏著力超過2 N/25 mm之前(換言之，於貼附後黏著力被抑制為2 N/25 mm以下之期間)進行。於該局部去除步驟S30中，使第一區域21殘留於被黏著體10上，並且將第二區域22自被黏著體10剝離去除。例如自黏著片材20之長度方向之一端朝向另一端剝離第二區域22。藉此，如圖2、3所示，形成由第一區域21所形成之黏著片21A、21B於被黏著體10上相互隔開地配置，於該等黏著片21A、21B之間露出被黏著體10的構造。The partial removal step S30 is before the adhesion of the adhesive sheet attached to the adherend to the adherend in the attaching step exceeds 2 N/25 mm (in other words, the adhesive force is suppressed to 2 N after the attachment) /25 mm or less). In the partial removal step S30, the first area 21 is left on the adherend 10, and the second area 22 is peeled and removed from the adherend 10. For example, the second region 22 is peeled off from one end of the adhesive sheet 20 in the longitudinal direction toward the other end. Thereby, as shown in FIGS. 2 and 3, the adhesive sheets 21A, 21B formed by the first region 21 are arranged to be separated from each other on the adherend 10, and the adhesive sheets 21A, 21B are exposed between the adhesive sheets 21A, 21B. The structure of the body 10.

本實施形態之積層體製造方法中，藉由在將黏著片材20貼附於被黏著體10後將該黏著片材20中之一部分、即第二區域22自被黏著體10剝離去除，而於被黏著體10上形成包含相互隔開地配置之兩片黏著片21A、21B之被覆圖案。根據該方法，可將積層體1中構成相互隔開之兩片黏著片21A、21B之第一區域21以一片黏著片材20之形態貼附於被黏著體10，且於貼附黏著片材20時，無需調整黏著片21A與黏著片21B之相對位置關係，藉此，積層體1之製造效率提高。又，由於在將黏著片材20貼附於被黏著體10後對該黏著片材20之第一區域21與第二區域22之邊界實施切斷處理，故而容易提高第一區域21之形狀精度或相對於被黏著體10之位置精度。例如，於貼附步驟S10中，黏著片材20相對於被黏著體10之貼附位置產生略微之偏移之情形、或者因溫度變化或內部應力之釋放等而導致黏著片材20產生略微之伸縮或變形之情形等時，亦可藉由調整切割步驟S20中之切斷處理之位置或形狀，而消除或減輕該等影響。In the method of manufacturing a laminated body of this embodiment, after the adhesive sheet 20 is attached to the adherend 10, a part of the adhesive sheet 20, that is, the second region 22 is peeled and removed from the adherend 10, and A coating pattern including two adhesive sheets 21A and 21B arranged apart from each other is formed on the adherend 10. According to this method, the first region 21 constituting the two separate adhesive sheets 21A, 21B in the laminated body 1 can be attached to the adherend 10 in the form of a single adhesive sheet 20, and then attached to the adhesive sheet At 20 o'clock, there is no need to adjust the relative positional relationship between the adhesive sheet 21A and the adhesive sheet 21B, thereby improving the manufacturing efficiency of the laminate 1. In addition, since the boundary between the first area 21 and the second area 22 of the adhesive sheet 20 is cut after the adhesive sheet 20 is attached to the adherend 10, it is easy to improve the shape accuracy of the first area 21 Or relative to the position accuracy of the adherend 10. For example, in the attaching step S10, the attachment position of the adhesive sheet 20 relative to the adherend 10 is slightly shifted, or the adhesive sheet 20 is slightly offset due to temperature changes or internal stress release. In the case of expansion or deformation, the position or shape of the cutting process in the cutting step S20 can also be adjusted to eliminate or reduce these effects.

上述製造方法中，製造黏著片21A、21B對被黏著體之黏著力為5 N/25 mm以上之積層體1。如此將黏著片21A、21B牢固地接合於被黏著體10就抑制於使用積層體1時因人之手接觸等外力、被黏著體之變形、或積層體被暴露於風雨或溫度變化等環境要因等而導致黏著片21A、21B自被黏著體10剝離或***之現象的觀點而言較佳。另一方面，於局部去除步驟S30中，若第二區域22對被黏著體10之黏著性過高，則可能產生於第二區域22剝離時被黏著體10產生伸長等變形或表面剝離等損傷、或第二區域22於剝離中途破裂等不良情況。根據上述製造方法，藉由在貼附步驟S10中貼附於被黏著體之黏著片材對該被黏著體之黏著力超過2 N/25 mm之前實施局部去除步驟S30，可製造黏著片21A、21B牢固地接合於被黏著體10之積層體1，且可於局部去除步驟S20中避免或減輕上述不良情況。In the above-mentioned manufacturing method, the laminated body 1 in which the adhesive force of the adhesive sheets 21A, 21B to the adherend is 5 N/25 mm or more is manufactured. Such adhesion of the adhesive sheets 21A, 21B to the adherend 10 firmly prevents the use of the laminated body 1 due to external forces such as human hand contact, deformation of the adherend, or exposure of the laminated body to environmental factors such as wind and rain or temperature changes. It is preferable from the viewpoint of the phenomenon that the adhesive sheets 21A and 21B peel off or bulge from the adherend 10. On the other hand, in the partial removal step S30, if the adhesion of the second region 22 to the adherend 10 is too high, it may be caused by deformation such as elongation of the adherend 10 or damage such as surface peeling when the second region 22 is peeled off. , Or the second region 22 is broken in the middle of peeling. According to the above manufacturing method, by performing the partial removal step S30 before the adhesion of the adhesive sheet attached to the adherend to the adherend in the attaching step S10 exceeds 2 N/25 mm, the adhesive sheet 21A, 21B is firmly bonded to the laminated body 1 of the adherend 10, and the above-mentioned disadvantages can be avoided or reduced in the partial removal step S20.

於若干種態樣中，關於局部去除步驟時之黏著片材對被黏著體之黏著力AP ，就第二區域之剝離容易性之觀點而言，例如可未達2 N/25 mm，可未達1.5 N/25 mm，可為1.3 N/25 mm以下，可為1 N/25 mm以下，亦可為0.8 N/25 mm以下。黏著力AP 之下限並無特別限制，就抑制切割步驟或局部去除步驟中之第一區域之位置偏移或***之觀點而言，例如可為0.005 N/25 mm以上，可為0.01 N/25 mm以上，可為0.05 N/25 mm以上，可為0.1 N/25 mm以上，亦可為0.2 N/25 mm以上。In several aspects, on the adhesive sheet when the step of partially removing the adhesion of the adhesion member P A, to release the second area of the viewpoint of easiness in terms of, for example less than 2 N / 25 mm, can be Less than 1.5 N/25 mm, can be 1.3 N/25 mm or less, can be 1 N/25 mm or less, or can be 0.8 N/25 mm or less. A P of the lower limit of adhesion is not particularly limited, the position of the viewpoint of suppressing the step of cutting the first area or partial removal of the step or ridge of the offset, for example, may be not less than 0.005 N / 25 mm, can be 0.01 N / 25 mm or more, it can be 0.05 N/25 mm or more, it can be 0.1 N/25 mm or more, or it can be 0.2 N/25 mm or more.

此處所揭示之製造方法可使用貼合於聚醯亞胺後於23℃下經過24小時後之黏著力(以下，亦稱為室溫24小時後黏著力)為2 N/25 mm以下的黏著片材良好地實施。根據此種黏著片材，可靈活地應對積層體之製造步驟之準備時間。上述室溫24小時後黏著力之上限例如可為與上述所例示之黏著力AP 之任一上限相同之程度。上述室溫24小時後黏著力之下限例如可為與上述所例示之黏著力AP 之任一下限相同之程度。The manufacturing method disclosed here can use the adhesive force (hereinafter, also referred to as the adhesive force after 24 hours at room temperature) of less than 2 N/25 mm after being laminated to polyimide at 23°C for 24 hours The sheet performs well. According to this adhesive sheet, it is possible to flexibly cope with the preparation time of the manufacturing step of the laminate. After 24 hours at room temperature the above-described upper limit for the adhesion of the same example of an upper limit with any of the illustrated A P of the above-described adhesion degree. The adhesion after 24 hours at room temperature the above-described lower limit, for example, may be any adhesive force A P of the embodiment shown and described above the lower limit of the same degree.

於實施局部去除步驟S30後，亦可視需要進而進行提高黏著片21A、21B對被黏著體10之黏著力之黏著力上升步驟S40。根據包括該黏著力上升步驟之製造方法，可縮短至獲得目標之積層體(即，黏著片對被黏著體之黏著力為5 N/25 mm以上之積層體)為止之期間。藉此，可提高積層體之生產性。又，藉由進行上述黏著力上升步驟，有製造出黏著片對被黏著體之黏著力更高之積層體之傾向。After the partial removal step S30 is implemented, the adhesive force increasing step S40 for improving the adhesive force of the adhesive sheets 21A, 21B to the adherend 10 can also be performed as needed. According to the manufacturing method including the step of increasing the adhesive force, the period until the target laminate (ie, the laminate with the adhesive sheet to the adherend is 5 N/25 mm or more) can be shortened. Thereby, the productivity of the laminate can be improved. In addition, by performing the above-mentioned adhesive force increasing step, there is a tendency to produce a laminated body with a higher adhesive force of the adhesive sheet to the adherend.

黏著力上升步驟S40可為賦予促進黏著片21A、21B之黏著力之上升之刺激的步驟。上述刺激之內容可對應於所使用之黏著片材之類型等而適當選擇。上述刺激之例可包含加熱、活性光線之照射、加壓(press)等。該等刺激可單獨應用一種或組合兩種以上應用。The adhesive force increasing step S40 may be a step of imparting a stimulus that promotes the increase of the adhesive force of the adhesive sheets 21A and 21B. The content of the above stimulus can be appropriately selected corresponding to the type of adhesive sheet used, etc. Examples of the above stimuli may include heating, irradiation of active light, press, and the like. These stimuli can be used alone or in combination of two or more applications.

再者，於此處所揭示之積層體製造方法中，黏著力上升步驟並非必需之步驟，係可考慮所使用之黏著片材之種類、所需之積層體之生產性或性能、該積層體之製造設備或製造成本等而適當採用之任意步驟。例如於藉由適當選擇積層體之製造所使用之黏著片材，而在局部去除步驟後不實施特別之黏著力上升步驟之態樣中，亦於黏著片材對被黏著體之黏著力超過2 N/25 mm之前進行局部去除步驟，且可製造出該黏著片材對上述被黏著體之黏著力為5 N/25 mm以上之積層體。Furthermore, in the laminated body manufacturing method disclosed here, the step of increasing the adhesion force is not a necessary step, and consideration can be given to the type of adhesive sheet used, the productivity or performance of the laminated body required, and the quality of the laminated body Any steps appropriately adopted for manufacturing equipment or manufacturing costs. For example, by appropriately selecting the adhesive sheet used in the manufacture of the laminate, but not performing a special adhesive force increasing step after the partial removal step, the adhesive force of the adhesive sheet to the adherend exceeds 2 A partial removal step is performed before N/25 mm, and a laminate with the adhesive sheet to the adherend above 5 N/25 mm can be manufactured.

藉由此處所揭示之方法所製造之積層體中所包含之黏著片包含基材層與黏著劑層，且經由上述黏著劑層接合於被黏著體。如此，於所獲得之積層體中利用黏著劑將黏著片與被黏著體接合、即黏著劑維持所需之黏彈性就藉由此處所揭示之方法所製造之積層體之柔軟性、耐衝擊性、應力緩和性、低溫特性、被黏著體與黏著片之密接性等觀點而言較佳。The adhesive sheet included in the laminated body manufactured by the method disclosed herein includes a base material layer and an adhesive layer, and is bonded to the adherend via the adhesive layer. In this way, the adhesive sheet and the adherend are joined with the adhesive in the obtained laminate, that is, the adhesive maintains the required viscoelasticity, and the flexibility and impact resistance of the laminate produced by the method disclosed here , Stress relaxation, low temperature characteristics, and adhesion between the adherend and the adhesive sheet are preferable.

再者，於圖2所示之例中，以覆蓋被黏著體10之單側之整面(全部區域)之方式貼附與該被黏著體10大致相同尺寸之黏著片材20，但黏著片材對被黏著體10之貼附態樣並不限定於此。例如可以黏著片材僅覆蓋被黏著體之單側之局部區域之方式貼附，亦可以黏著片材之一部分自被黏著體伸出之方式貼附。又，於貼附步驟S10所使用之黏著片材中，第一區域與第二區域只要以可將該等區域作為連續之片材操作之程度相連即可，於該範圍內，可在第一區域與第二區域之邊界設置有切縫(穿孔等)、半切等切斷輔助構造。此處，所謂半切係指不將黏著片材於厚度方向上貫通之深度之切口，典型而言，以不將基材層於厚度方向上貫通之深度之切口之形式形成。此種切口例如可藉由使加工刀自基材層之背面(與積層黏著劑層之側相反之側)進入至未貫通該基材層之深度而形成。於一態樣中，就提高黏著片材之操作性或降低製造成本等觀點而言，可良好地使用未於第一區域與第二區域之邊界設置切斷輔助構造之黏著片材。又，亦可於貼附步驟S10所使用之黏著片材設置有助於該黏著片材與被黏著體之位置對準之記號。上述記號可為如貫通孔、切口、凹陷等之構造性記號，可為由能夠進行光學檢測之標記(例如印刷或著色)等所形成之視覺性記號，亦可為基於不同構件之配置(例如識別標籤之貼附、能夠發送或反射信號之元件之固定)者。此種記號可設置於第一區域及第二區域之一者或兩者，亦可設置於第一區域與第二區域之邊界。Furthermore, in the example shown in FIG. 2, the adhesive sheet 20 of approximately the same size as the adherend 10 is attached to cover the entire surface (the entire area) of one side of the adherend 10, but the adhesive sheet The attachment state of the material to the adherend 10 is not limited to this. For example, the adhesive sheet can be attached in a manner that only covers a partial area of one side of the adherend, or it can be attached in a manner that a part of the adhesive sheet protrudes from the adherend. In addition, in the adhesive sheet used in the attaching step S10, the first area and the second area only need to be connected to the extent that these areas can be operated as a continuous sheet. Within this range, the first area can be The boundary between the area and the second area is provided with cutting auxiliary structures such as slits (perforations, etc.) and half-cuts. Here, the so-called half-cut refers to a deep cut that does not penetrate the adhesive sheet in the thickness direction, and is typically formed as a deep cut that does not penetrate the base layer in the thickness direction. Such a cut can be formed, for example, by inserting a processing knife from the back surface of the base material layer (the side opposite to the side where the adhesive layer is laminated) to a depth that does not penetrate the base material layer. In one aspect, from the viewpoint of improving the operability of the adhesive sheet or reducing the manufacturing cost, the adhesive sheet without the cutting auxiliary structure provided on the boundary between the first area and the second area can be used well. In addition, the adhesive sheet used in the attaching step S10 may also be provided with a mark that helps the position of the adhesive sheet and the adherend to be aligned. The above-mentioned marks may be structural marks such as through holes, cuts, depressions, etc., may be visual marks formed by optically detectable marks (such as printing or coloring), etc., or may be based on the configuration of different components (such as The attachment of identification tags, the fixing of components capable of sending or reflecting signals). Such a mark can be provided in one or both of the first area and the second area, and can also be provided at the boundary between the first area and the second area.

又，於圖4所示之例中，切割步驟S20中，以貫通黏著片材至被黏著體表面之深度實施連續之線狀之切斷加工，但切斷加工之態樣並不限定於此。例如，亦可以可適當地實施局部去除步驟S30之限度將切割步驟S20後之第一區域與第二區域局部地相連。作為此種切斷加工之例，可列舉：穿孔等不連續之切斷加工、半切加工、將穿孔與半切組合之加工(例如交替地重複貫通基材層之切縫與不貫通該基材層之深度之切口之態樣之切斷加工)等。又，上述切斷加工可以貫通黏著片材至被黏著體表面之深度進行，亦可以貫通黏著片材且進而自被黏著體之表面到達一部分深度為止之方式進行，亦可以不貫通黏著片材之深度(即半切)進行。於此處所揭示之製造方法中，於進行局部去除步驟S30時，可將黏著片材對被黏著體之黏著力抑制為較低，因此較佳為以將第一區域與第二區域完全分離之方式進行切斷加工至至少貫通基材層之深度為止。該情況就提高局部去除步驟S30中之第二區域之拾取性、第一區域之***或偏移防止性、提高第一區域之外形精度等觀點而言可能變得有利。In the example shown in FIG. 4, in the cutting step S20, a continuous linear cutting process is performed at a depth that penetrates the adhesive sheet to the surface of the adherend, but the cutting process is not limited to this . For example, the limit of the partial removal step S30 may be appropriately implemented to locally connect the first area and the second area after the cutting step S20. Examples of such cutting processing include: discontinuous cutting processing such as perforation, half-cut processing, and processing that combines perforation and half-cutting (for example, alternately repeating slits penetrating the base material layer and not penetrating the base material layer The cutting process of the depth of the incision), etc. In addition, the above-mentioned cutting process may be carried out through the adhesive sheet to the depth of the surface of the adherend, or through the adhesive sheet and then from the surface of the adherend to a part of the depth, or it may not penetrate through the adhesive sheet. Deep (ie half-cut). In the manufacturing method disclosed herein, when performing the partial removal step S30, the adhesive force of the adhesive sheet to the adherend can be suppressed to be low. Therefore, it is preferable to completely separate the first region from the second region The cutting process is carried out to at least the depth of the substrate layer. This situation may become advantageous from the viewpoints of improving the pick-up properties of the second region in the partial removal step S30, the prevention of bulging or shifting of the first region, and improving the shape accuracy of the first region.

於圖4所示之例中，呈直線狀延伸之第二區域之一端及另一端到達黏著片材之端。如此以第二區域之至少一端到達黏著片材之端之方式設定該第二區域就局部去除步驟S30中之第二區域之拾取性之觀點而言較佳。於第二區域未到達黏著片材之端之態樣中，例如可藉由在第二區域之一端，於該第二區域之背面貼附強黏著性之黏著帶並提拉而進行第二區域之拾取。該拾取方法亦可用於第二區域之至少一端到達黏著片材之端之態樣。於此處所揭示之積層體製造方法中，局部去除步驟時之黏著片材對上述被黏著體之黏著力為2 N/25 mm以下就藉由如上所述貼附黏著帶並提拉之方法提高第二區域之拾取性之觀點而言有利。In the example shown in FIG. 4, one end and the other end of the second region extending linearly reach the end of the adhesive sheet. In this way, it is better to set the second area so that at least one end of the second area reaches the end of the adhesive sheet, from the viewpoint of the pick-up property of the second area in the partial removal step S30. In the state where the second area does not reach the end of the adhesive sheet, for example, the second area can be performed by attaching a strong adhesive tape to the back of the second area at one end of the second area and pulling it up. The pickup. This picking method can also be used in a state where at least one end of the second area reaches the end of the adhesive sheet. In the laminated body manufacturing method disclosed here, the adhesion of the adhesive sheet to the adherend in the partial removal step is 2 N/25 mm or less, which is improved by attaching the adhesive tape and pulling it as described above. It is advantageous from the viewpoint of the pick-up of the second area.

於以第二區域到達黏著片材之端之方式設定之態樣中，就拾取性之觀點而言，上述第二區域到達上述黏著片材之端之寬度較佳為設為0.2 mm以上，可為0.5 mm以上，亦可為1 mm以上。為了提高拾取性，亦可構成為，於第二區域到達黏著片材之端之附近，該第二區域之寬度擴大。又，就包含藉由此處所揭示之製造方法所獲得之積層體之製品(電子裝置等)之小型化之觀點而言，上述第二區域到達上述黏著片材之端之寬度較佳為設為10 mm以下，進而較佳為設為8 mm以下。In the aspect set in such a way that the second area reaches the end of the adhesive sheet, from the viewpoint of pick-up property, the width of the second area to the end of the adhesive sheet is preferably set to 0.2 mm or more. It is 0.5 mm or more, or 1 mm or more. In order to improve the pick-up property, it can also be configured that the width of the second area is enlarged near the end of the adhesive sheet in the second area. In addition, from the viewpoint of miniaturization of products (electronic devices, etc.) including a laminate obtained by the manufacturing method disclosed herein, the width of the second region reaching the end of the adhesive sheet is preferably set to 10 mm or less, more preferably 8 mm or less.

於此處所揭示之積層體製造方法包括黏著力上升步驟之情形時，該步驟中使黏著力上升之程度並無特別限定，與該步驟前之黏著力相比，該步驟後之黏著力或經由該步驟所獲得之積層體之黏著力相對變高即可。於若干種態樣中，黏著力上升步驟較佳為以該步驟前之對被黏著體之黏著力A0 [N/25 mm]與該步驟後之對被黏著體之黏著力A1 [N/25 mm]的關係滿足比(A1 /A0 )≧2之方式進行。即，於黏著力上升步驟中，較佳為使黏著片材對被黏著體之黏著力上升至該步驟前之2倍以上。根據此種黏著力上升步驟，有良好地同時實現局部去除步驟中之第二區域之去除容易性與所製造之積層體之黏著片對被黏著體之強黏著性之傾向。於若干種態樣中，上述比(A1 /A0 )例如可為3以上，可為5以上，亦可為10以上。上述比(A1 /A0 )之上限並無特別限制，就抑制黏著力上升步驟前之第一區域之位置偏移或***之觀點而言，通常較佳為10000以下、5000以下或2000以下。上述黏著力A0 、A1 之各者可藉由依據JIS Z0237，於23℃、50%RH之環境下，於剝離角度180度、拉伸速度300 mm/min之條件下，測定黏著片材自被黏著體之剝離強度而把握。In the case where the manufacturing method of the laminate disclosed here includes the step of increasing the adhesion force, the degree of the increase of the adhesion force in this step is not particularly limited. Compared with the adhesion force before the step, the adhesion force after the step or through The adhesive force of the laminated body obtained in this step can be relatively high. In some aspects, the adhesion increasing step is preferably based on the adhesion force A 0 [N/25 mm] to the adherend before the step and the adhesion force A 1 [N] to the adherend after the step /25 mm] The relationship satisfies the ratio (A 1 /A 0 )≧2. That is, in the step of increasing the adhesive force, it is preferable to increase the adhesive force of the adhesive sheet to the adherend to more than 2 times of that before the step. According to this step of increasing the adhesion force, there is a tendency to achieve both the ease of removal of the second area in the partial removal step and the strong adhesion of the adhesive sheet of the manufactured laminate to the adherend. In some aspects, the above ratio (A 1 /A 0 ) may be 3 or more, 5 or more, or 10 or more, for example. The upper limit of the above-mentioned ratio (A 1 /A 0 ) is not particularly limited. From the viewpoint of suppressing the positional deviation or uplift of the first region before the step of increasing the adhesive force, it is generally preferably 10000 or less, 5000 or less or 2000 or less . Each of the above-mentioned adhesive forces A 0 and A 1 can be measured on the adhesive sheet under the conditions of 23°C and 50%RH under the conditions of peeling angle of 180° and stretching speed of 300 mm/min in accordance with JIS Z0237 From the peel strength of the adherend.

黏著力上升步驟前之黏著片材對被黏著體之黏著力A0 例如可為與上述局部去除步驟時之黏著力AP 大致相同之程度。因此，上述所例示之黏著力AP 之各上限值及各下限值亦可分別獨立地應用於黏著力A0 可採用之上限值及下限值之各者。又，上述所例示之黏著力AP 之各上限值及下限值亦可分別獨立地應用於下述初期黏著力B0 可採用之上限值及下限值之各者。Before the adhesive sheet for adhesion of the rising steps A 0 is the adhesion of the adhesive material of the adhesive force may be, for example, when the above-described step A P partially removed of substantially the same degree. Therefore, the upper limits and each of the above-exemplified adhesion value of P A each independently may be applied over the adhesive force A 0 may be employed by each of the limit value and the lower limit. Further, each of the upper limit value and the lower limit of the above-exemplified adhesion of A P may be applied independently to each of the following initial adhesion on B 0 may be used by each of the limit value and the lower limit.

於藉由此處所揭示之方法所製造之積層體中，黏著片對被黏著體之黏著力AF 例如可超過5 N/25 mm，可為7 N/25 mm以上，可為10 N/25 mm以上，亦可為12 N/25 mm以上。就抑制使用上述積層體時之黏著片自被黏著體之剝離或***之觀點而言，較佳為黏著力AF 較高。黏著力AF 之上限並無特別限制。就容易兼顧到局部去除步驟中之第二區域之剝離容易性之觀點而言，於若干種態樣中，黏著力AF 例如可為50 N/25 mm以下，可為40 N/25 mm以下，可為35 N/25 mm以下，亦可為30 N/25 mm以下。In the laminated body manufactured by the method disclosed here, the adhesive force A F of the adhesive sheet to the adherend may exceed 5 N/25 mm, may be more than 7 N/25 mm, or may be 10 N/25 mm or more, but also 12 N/25 mm or more. From the viewpoint of suppressing peeling or swelling of the adhesive sheet from the adherend when the above-mentioned laminated body is used, it is preferable that the adhesive force A F is higher. The upper limit of the adhesive force A F is not particularly limited. From the point of view that it is easy to take into account the ease of peeling of the second area in the partial removal step, in several aspects, the adhesion force A F can be 50 N/25 mm or less, for example, 40 N/25 mm or less , Can be 35 N/25 mm or less, or 30 N/25 mm or less.

再者，於包含黏著力上升步驟之態樣中，該黏著力上升步驟後之黏著片材對被黏著體之黏著力A1 [N/25 mm]例如可為與所製造之積層體之黏著片對被黏著體之黏著力AF 大致相同之程度。因此，上述所例示之黏著力AF 之各上限值及各下限值亦可分別獨立地應用於黏著力A1 可採用之上限值及下限值之各者。又，上述所例示之黏著力AF 之各上限值及下限值亦可分別獨立地應用於下述刺激後黏著力B1 可採用之上限值及下限值之各者。Furthermore, in the aspect including the adhesive force increasing step, the adhesive force A 1 [N/25 mm] of the adhesive sheet to the adherend after the adhesive force increasing step may be, for example, the adhesion with the manufactured laminate The adhesive force A F of the sheet to the adherend is approximately the same degree. Therefore, each upper limit and each lower limit of the adhesive force A F exemplified above can also be independently applied to each of the upper limit and the lower limit that the adhesive force A 1 can adopt. In addition, each of the upper limit and lower limit of the adhesion force A F exemplified above can also be independently applied to each of the following post-stimulation adhesion force B 1 which can adopt the upper limit and the lower limit.

黏著力上升步驟中對黏著片材賦予之刺激之內容例如可以如下方式設定，即，以所使用之黏著片材對聚醯亞胺之初期黏著力B0 相對於刺激後黏著力B1 的比之形式定義之黏著力上升比(B1 /B0 )滿足特定之目標值。初期黏著力B0 及刺激後黏著力B1 係藉由下述實施例所記載之方法進行測定。The content of the stimulus imparted to the adhesive sheet in the step of increasing the adhesive force can be set, for example, by the ratio of the initial adhesive force B 0 of the adhesive sheet used to the polyimide to the post-stimulus adhesive force B 1 The increase ratio of adhesion force (B 1 /B 0 ) defined by the form meets a specific target value. The initial adhesive force B 0 and the post-stimulation adhesive force B 1 were measured by the method described in the following examples.

於此處所揭示之製造方法包括黏著力上升步驟之情形時，該黏著力上升步驟較佳為以黏著力上升比(B1 /B0 )成為例如2以上之方式進行，更佳為以黏著力上升比(B1 /B0 )成為3以上、5以上、10以上或15以上之方式進行。又，就減輕對黏著片材及被黏著體施加之負載或提高積層體之生產性之觀點而言，黏著力上升步驟可以黏著力上升比(B1 /B0 )成為約10000以下、5000以下或2000以下之方式實施。於若干種態樣中，黏著力上升比(B1 /B0 )例如可為1000以下，可為500以下，可為200以下，亦可為100以下。In the case where the manufacturing method disclosed here includes an adhesive force increasing step, the adhesive force increasing step is preferably performed in such a way that the adhesive force increasing ratio (B 1 /B 0 ) becomes, for example, 2 or more, more preferably with the adhesive force The increase ratio (B 1 /B 0 ) is 3 or more, 5 or more, 10 or more, or 15 or more. In addition, from the viewpoint of reducing the load applied to the adhesive sheet and the adherend or improving the productivity of the laminate, the adhesive force increase step can make the adhesive force increase ratio (B 1 /B 0 ) approximately 10000 or less and 5000 or less Or implementation under 2000. In some aspects, the adhesion increase ratio (B 1 /B 0 ) may be 1000 or less, 500 or less, 200 or less, or 100 or less, for example.

又，於可撓性顯示面板、可撓性印刷配線板(FPC)、將顯示面板與配線板一體化而成之裝置等中，使用可撓性基板材料，就耐熱性或尺寸穩定性之觀點而言，多數情況下使用聚醯亞胺膜作為上述基板材料。對於聚醯亞胺顯示上述黏著力B0 、B1 或黏著力上升比(B1 /B0 )之黏著片材係以將聚醯亞胺作為被黏著體之態樣用於積層體之製造，於局部去除步驟中，第二區域之剝離作業性良好，且於使用所獲得之積層體時，可發揮與被黏著體之接著可靠性優異之性質。利用該性質，可高精度且高效率地形成FPC之膜覆蓋層。因此，此處所揭示之方法例如可良好地應用於具備膜覆蓋層之FPC之製造。In addition, flexible substrate materials are used in flexible display panels, flexible printed wiring boards (FPC), devices that integrate display panels and wiring boards, etc., from the viewpoint of heat resistance or dimensional stability In general, polyimide film is used as the above-mentioned substrate material in most cases. For polyimide, the adhesive sheet that shows the above-mentioned adhesive force B 0 , B 1 or the increase ratio of adhesive force (B 1 /B 0 ) is to use polyimide as the adhered body for the manufacture of laminated body In the partial removal step, the peeling workability of the second area is good, and when the obtained laminate is used, it can exhibit the property of excellent adhesion with the adherend. Utilizing this property, the film coating layer of FPC can be formed with high precision and high efficiency. Therefore, the method disclosed here can be suitably applied to the manufacture of FPC with a film cover layer, for example.

於黏著力上升步驟中進行加熱作為對黏著片材賦予之刺激之情形時之加熱溫度並無特別限定，可考慮作業性、經濟性、黏著片材中可包含之基材層或被黏著體之耐熱性等而進行設定。上述加熱溫度例如可未達150℃，可為120℃以下，可為100℃以下，可為80℃以下，亦可為70℃以下。又，上述加熱溫度例如可設為40℃以上、50℃以上或60℃以上，可設為80℃以上，亦可設為100℃以上。根據更高之加熱溫度，可藉由更短時間之處理使黏著力上升。加熱時間並無特別限定，例如可為1小時以下，可為30分鐘以下，可為10分鐘以下，亦可為5分鐘以下。或者，亦可以黏著片材或被黏著體不會產生顯著之熱劣化之限度，進行更長時間之(例如2小時以上、5小時以上等之)加熱處理。再者，加熱處理可一次進行，亦可分為複數次進行。The heating temperature in the case of heating as a stimulus to the adhesive sheet in the step of increasing the adhesive force is not particularly limited, and consideration can be given to workability, economy, and the substrate layer or the adherend that can be included in the adhesive sheet Set the heat resistance, etc. For example, the heating temperature may not reach 150°C, may be 120°C or lower, may be 100°C or lower, may be 80°C or lower, or may be 70°C or lower. In addition, the heating temperature can be set to 40°C or higher, 50°C or higher, or 60°C or higher, for example, 80°C or higher, or 100°C or higher. According to the higher heating temperature, the adhesive force can be increased by the shorter time treatment. The heating time is not particularly limited. For example, it may be 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less. Alternatively, the adhesive sheet or the adherend can be heated for a longer period of time (for example, 2 hours or more, 5 hours or more, etc.) to the extent that there is no significant thermal deterioration. In addition, the heat treatment may be performed at one time or may be divided into multiple times.

貼附步驟所使用之黏著片材可於一片黏著片材中僅包含一個成為構成積層體之黏著片之區域(第一區域)，例如可如圖2所示包含相互隔開之兩個第一區域，亦可包含三個以上之第一區域。於一片黏著片材包含複數個第一區域之情形時，該等第一區域之形狀可相同亦可不同。同樣地，貼附步驟所使用之黏著片材於一片黏著片材中，例如可如圖4所示僅包含一個局部去除步驟中會被剝離去除之第二區域，亦可包含兩個以上或三個以上。於一片黏著片材包含複數個第二區域之情形時，該等第二區域之形狀可相同亦可不同。The adhesive sheet used in the attaching step may include only one area (first area) that becomes the adhesive sheet constituting the laminate in one adhesive sheet. For example, it may include two first areas separated from each other as shown in FIG. 2 The area may also include more than three first areas. When an adhesive sheet includes a plurality of first regions, the shapes of the first regions may be the same or different. Similarly, the adhesive sheet used in the attaching step in one adhesive sheet, for example, may include only one second area that will be peeled off in the partial removal step as shown in FIG. 4, or may include more than two or three More than one. When an adhesive sheet includes a plurality of second regions, the shapes of the second regions may be the same or different.

於若干種態樣之積層體製造方法中，作為貼附步驟所使用之黏著片材及被黏著體，可使用包含複數個與藉由該方法所製造之積層體對應之單元者。該態樣可進而包括將上述黏著片材及上述被黏著體分割為上述單元之分割步驟作為上述貼附步驟之後進行之步驟。上述分割步驟可於進行貼附步驟後於任意之時期進行。例如，可藉由在至少結束切割步驟後進行分割步驟，而針對複數個單元統一進行切割步驟。此處所揭示之製造方法例如可以(a)於切割步驟與局部去除步驟之間包括上述分割步驟之態樣實施。於在局部去除步驟後包括黏著力上升步驟之製造方法中，例如亦可以(b)於局部去除步驟與黏著力上升步驟之間或(c)於黏著力上升步驟後包括上述分割步驟之態樣實施。亦可使用上述(a)～(c)之態樣之一種或組合兩種以上。再者，上述態樣(a)例如可使用具備下述黏著劑層(2)之黏著片材良好地實施。上述態樣(b)或上述態樣(c)例如可使用具備下述黏著劑層(1)或黏著劑層(2)之黏著片材良好地實施。In several types of laminated body manufacturing methods, as the adhesive sheet and the adherend used in the attaching step, one containing a plurality of units corresponding to the laminated body manufactured by this method can be used. This aspect may further include a step of dividing the adhesive sheet and the adherend into the units as a step performed after the attaching step. The above dividing step can be performed at any time after the attaching step. For example, by performing the dividing step after at least the cutting step is completed, the cutting step can be performed uniformly for a plurality of units. The manufacturing method disclosed herein can be implemented, for example (a) including the above-mentioned dividing step between the cutting step and the partial removal step. In a manufacturing method that includes an adhesive force increasing step after the partial removal step, for example, (b) between the partial removal step and the adhesive force increasing step or (c) after the adhesive force increasing step may include the above-mentioned dividing step Implement. One or a combination of two or more of the above-mentioned (a) to (c) can also be used. Furthermore, the above aspect (a) can be implemented satisfactorily using, for example, an adhesive sheet provided with the following adhesive layer (2). The above aspect (b) or the above aspect (c) can be implemented satisfactorily using, for example, an adhesive sheet provided with the following adhesive layer (1) or adhesive layer (2).

＜＜製造裝置＞＞ 例如圖5所示，此處所揭示之積層體製造方法可使用積層體製造裝置50實施，該積層體製造裝置50具備：貼附機構51，其係將黏著片材20貼附於被黏著體10；切割機構52，其係對黏著片材20之第一區域21與第二區域22之邊界實施切斷加工；及剝離機構53，其係使第一區域21殘留於被黏著體10上並且將第二區域22自被黏著體10剝離去除。＜＜Manufacturing equipment＞＞ For example, as shown in FIG. 5, the laminated body manufacturing method disclosed here can be implemented using a laminated body manufacturing apparatus 50, which is provided with an attaching mechanism 51 for attaching the adhesive sheet 20 to the adherend 10 The cutting mechanism 52, which cuts the boundary between the first area 21 and the second area 22 of the adhesive sheet 20; and the peeling mechanism 53, which leaves the first area 21 on the adherend 10 and will The second region 22 is peeled and removed from the adherend 10.

貼附機構51以可實施此處所揭示之任一製造方法中之貼附步驟之方式構成，例如可包含被黏著體供給部件、黏著片材供給部件、黏著片材對被黏著體之壓接部件等之一種或兩種以上。切割機構52以可實施此處所揭示之任一製造方法中之切割步驟之方式構成，可包含如上述所例示之切斷部件之一種或兩種以上。剝離機構53以可實施此處所揭示之任一方法中之局部去除步驟之方式構成，例如可包含第二區域之拾取部件、保持部件、剝離部件等之一種或兩種以上。The attaching mechanism 51 is configured to perform the attaching step in any of the manufacturing methods disclosed herein, and may include, for example, an adherend supply member, an adhesive sheet supply member, and a pressure bonding member between the adhesive sheet and the adherend. One or more than two. The cutting mechanism 52 is configured to implement the cutting steps in any of the manufacturing methods disclosed herein, and may include one or two or more of the cutting components exemplified above. The peeling mechanism 53 is configured in a manner that can implement the partial removal steps in any of the methods disclosed herein, and may include, for example, one or two or more of the pickup member, the holding member, and the peeling member of the second region.

再者，包含黏著力上升步驟之態樣之積層體製造方法之實施可使用之積層體製造裝置例如可進而包含未圖示之黏著力上升機構作為對第一區域賦予使其黏著力上升之刺激之機構。黏著力上升機構構成為，藉由對黏著片材提供可使該黏著片材之黏著力上升之刺激，可實施此處所揭示之任一方法中之黏著力上升步驟。黏著力上升機構例如可包含UV(ultraviolet，紫外線)照射部件(UV照射燈、光路調整用鏡等)、加熱部件(熱風加熱器、紅外線加熱器、電熱器等)、加壓部件等之一種或兩種以上。 又，包含分割步驟之態樣之積層體製造方法所使用之製造裝置可進而包含未圖示之分割機構。上述分割機構可構成為，可使用利用湯姆森刀或尖刀、旋轉刀、切刀(knife)等之切斷、或雷射切斷、噴水式切斷、刀片(blade)切斷等公知之分割方法實施分割步驟。Furthermore, the laminated body manufacturing apparatus that can be used for the implementation of the laminated body manufacturing method including the step of increasing the adhesive force may further include, for example, an adhesive force increasing mechanism not shown as a stimulus to increase the adhesive force of the first region的机构。 Institutions. The adhesive force increasing mechanism is configured to provide a stimulus to the adhesive sheet to increase the adhesive force of the adhesive sheet, so that the adhesive force increasing step in any method disclosed herein can be implemented. The adhesion-increasing mechanism may include, for example, one of UV (ultraviolet) irradiation components (UV irradiation lamps, optical path adjustment mirrors, etc.), heating components (hot air heaters, infrared heaters, electric heaters, etc.), pressure components, etc. Two or more. Furthermore, the manufacturing apparatus used in the laminated body manufacturing method of the aspect including the dividing step may further include a dividing mechanism not shown. The above-mentioned dividing mechanism may be configured to use known dividing methods such as Thomson knife, sharp knife, rotary knife, knife, etc., or laser cutting, water jet cutting, blade cutting, etc. The method implements the segmentation step.

＜＜黏著片材＞＞ 以下，對可良好地用以實施此處所揭示之積層體製造方法的黏著片材之若干例進行說明，但並非意欲限定本發明之範圍。＜＜Adhesive sheet＞＞ Hereinafter, some examples of adhesive sheets that can be used to implement the laminated body manufacturing method disclosed here are described, but they are not intended to limit the scope of the present invention.

此處所揭示之積層體製造方法可使用包含基材層與積層於該基材層之至少被黏著體側之黏著劑層的構成之黏著片材良好地實施。根據黏著劑層積層於基材層之構成之黏著片材，可藉由上述基材層補強黏著劑層，因此於局部去除步驟中容易自被黏著體剝離第二區域。The laminated body manufacturing method disclosed here can be implemented satisfactorily using an adhesive sheet composed of a substrate layer and an adhesive layer laminated on at least the adherend side of the substrate layer. According to the adhesive sheet composed of the adhesive layered on the substrate layer, the adhesive layer can be reinforced by the above-mentioned substrate layer, so that the second area is easily peeled from the adherend in the partial removal step.

＜基材層＞ 作為上述基材層，可良好地使用各種膜基材。上述膜基材可如發泡體膜或不織布片材等般為多孔質基材，可為非多孔質基材，亦可為多孔質層與非多孔質層積層而成之構造之基材。於若干種態樣中，作為上述膜基材，可良好地使用含有能夠獨立地維持形狀之(自立型或非依存性之)樹脂膜作為基底膜者。此處所謂「樹脂膜」，意指為非多孔質構造且典型而言實質上不包含氣泡之(無空隙之)樹脂膜。因此，上述樹脂膜之概念區別於發泡體膜或不織布。上述樹脂膜可為單層構造，亦可為兩層以上之多層構造(例如三層構造)。＜Base layer＞ As the substrate layer, various film substrates can be used favorably. The film substrate may be a porous substrate such as a foam film or a non-woven fabric sheet, may be a non-porous substrate, or may be a substrate with a structure in which a porous layer and a non-porous layer are laminated. In some aspects, as the above-mentioned film base material, a base film containing a (self-supporting or non-dependent) resin film capable of independently maintaining a shape can be preferably used. The "resin film" used here means a resin film that has a non-porous structure and typically does not substantially contain air bubbles (no voids). Therefore, the above-mentioned concept of resin film is different from foam film or nonwoven fabric. The above-mentioned resin film may have a single-layer structure or a multilayer structure of two or more layers (for example, a three-layer structure).

作為構成樹脂膜之樹脂材料，例如可使用：聚酯、聚烯烴、尼龍6、尼龍66、部分芳香族聚醯胺等聚醯胺(PA)、聚醯亞胺(PI)、聚醯胺醯亞胺(PAI)、聚醚醚酮(PEEK)、聚醚碸(PES)、聚苯硫醚(PPS)、聚碳酸酯(PC)、聚胺基甲酸酯(PU)、乙烯-乙酸乙烯酯共聚物(EVA)、聚四氟乙烯(PTFE)等氟樹脂、丙烯酸系樹脂、聚丙烯酸酯、聚苯乙烯、聚氯乙烯、聚偏二氯乙烯等樹脂。As the resin material constituting the resin film, for example, polyamide (PA) such as polyester, polyolefin, nylon 6, nylon 66, partially aromatic polyamide, polyimide (PI), and polyamide can be used. Imine (PAI), polyether ether ketone (PEEK), polyether ether (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate Fluorine resin such as ester copolymer (EVA) and polytetrafluoroethylene (PTFE), acrylic resin, polyacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride and other resins.

上述樹脂膜可為使用單獨含有此種樹脂之一種之樹脂材料所形成者，亦可為使用摻合有兩種以上之樹脂材料所形成者。上述樹脂膜可未經延伸，亦可為經延伸(例如單軸延伸或雙軸延伸)者。例如可良好地使用聚對苯二甲酸乙二酯(PET)膜、聚萘二甲酸乙二酯(PEN)膜、無延伸聚丙烯(CPP)膜、雙軸延伸聚丙烯(OPP)膜、低密度聚乙烯(LDPE)膜、直鏈狀低密度聚乙烯(LLDPE)膜、PP/PE摻合膜等樹脂膜。作為就強度或尺寸穩定性之觀點而言較佳之樹脂膜之例，可列舉PET膜、PEN膜、PPS膜及PEEK膜。就獲取容易性等觀點而言，尤佳為PET膜及PPS膜，其中較佳為PET膜。The above-mentioned resin film may be formed using a resin material containing one kind of such resin alone, or may be formed using a resin material blended with two or more kinds of resin. The aforementioned resin film may not be stretched, or may be stretched (for example, uniaxially stretched or biaxially stretched). For example, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, non-stretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low Resin films such as density polyethylene (LDPE) film, linear low-density polyethylene (LLDPE) film, PP/PE blended film, etc. As an example of a preferable resin film from the viewpoint of strength or dimensional stability, a PET film, a PEN film, a PPS film, and a PEEK film can be cited. From the standpoint of availability and the like, PET films and PPS films are particularly preferred, and among them, PET films are preferred.

於樹脂膜中，可於不明顯阻礙本發明之效果之範圍內，視需要調配光穩定劑、抗氧化劑、抗靜電劑、著色劑(染料、顏料等)、填充材、滑澤劑、抗黏連劑等公知添加劑。In the resin film, light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, lubricants, and anti-sticking agents can be blended as needed within the range that does not significantly hinder the effects of the present invention. Well-known additives such as joint agents.

樹脂膜之製造方法並無特別限定。例如可適當採用擠出成形、吹脹成形、T模流延成形、砑光輥成形等先前公知之一般之樹脂膜成形方法。The manufacturing method of the resin film is not specifically limited. For example, conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be suitably used.

上述基材層可為實質上由此種基底膜構成者。或者，上述基材層亦可為除包含上述基底膜以外，亦包含輔助層者。作為上述輔助層之例，可列舉：光學特性調整層(例如著色層、抗反射層)、用以對基材層賦予所需之外觀之印刷層或層壓層、抗靜電層、底塗層、剝離層等表面處理層。The above-mentioned base material layer may consist essentially of such a base film. Alternatively, the base material layer may include an auxiliary layer in addition to the base film. Examples of the above-mentioned auxiliary layer include: an optical property adjustment layer (for example, a coloring layer, an anti-reflection layer), a printing layer or a laminate layer for giving the base layer a desired appearance, an antistatic layer, and a primer layer , Surface treatment layer such as peeling layer.

對於基材層中積層黏著劑層之側之面，亦可視需要實施電暈放電處理、電漿處理、紫外線照射處理、酸處理、鹼處理、利用底塗劑(primer)之塗佈之底塗層之形成等先前公知之表面處理。此種表面處理可為用以提高黏著劑層對基材層之抓固性之處理。用於底塗層之形成之底塗劑之組成並無特別限定，可自公知者適當選擇。底塗層之厚度並無特別限制，通常適宜為0.01 μm～1 μm左右，較佳為0.1 μm～1 μm左右。作為可視需要對基材層實施之其他處理，可列舉抗靜電層形成處理、著色層形成處理、印刷處理等。該等處理可單獨應用或組合應用。For the substrate layer on the side of the laminated adhesive layer, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and primer coating with primer The formation of the layer and other previously known surface treatments. Such surface treatment can be used to improve the grip of the adhesive layer to the substrate layer. The composition of the primer used for the formation of the primer layer is not particularly limited, and can be appropriately selected from known ones. The thickness of the primer layer is not particularly limited, but it is usually about 0.01 μm to 1 μm, preferably about 0.1 μm to 1 μm. As other treatments that may be performed on the base material layer as needed, antistatic layer formation treatment, colored layer formation treatment, printing treatment, etc. can be cited. These treatments can be applied individually or in combination.

＜＜黏著劑層＞＞ 構成黏著劑層之黏著劑之組成並無特別限定。上述黏著劑可為含有黏著劑之領域中公知之丙烯酸系聚合物、橡膠系聚合物、聚酯系聚合物、胺基甲酸酯系聚合物、聚醚系聚合物、聚矽氧系聚合物、聚醯胺系聚合物、氟系聚合物等之於室溫區域顯示橡膠彈性之各種聚合物之一種或兩種以上作為基礎聚合物(聚合物成分中之主成分、即佔據超過50重量%之成分)者。其中，作為較佳之黏著劑，可例示丙烯酸系黏著劑及橡膠系黏著劑。此處，所謂丙烯酸系黏著劑係指含有丙烯酸系聚合物作為基礎聚合物之黏著劑。關於橡膠系黏著劑亦同樣如此。又，上述所謂丙烯酸系聚合物係指構成該丙烯酸系聚合物之單體成分總量中之50重量%以上為丙烯酸系單體之聚合物。再者，本說明書中，所謂丙烯酸系單體係指於1分子中具有至少一個(甲基)丙烯醯基之單體。又，上述所謂(甲基)丙烯醯基係包括丙烯醯基及甲基丙烯醯基之含義。＜＜Adhesive layer＞＞ The composition of the adhesive constituting the adhesive layer is not particularly limited. The above-mentioned adhesive may be acrylic polymer, rubber polymer, polyester polymer, urethane polymer, polyether polymer, silicone polymer, One or two or more of various polymers that exhibit rubber elasticity in the room temperature region, such as polyamide-based polymers and fluorine-based polymers, are used as the base polymer (the main component of the polymer component, that is, more than 50% by weight) Ingredients). Among them, as preferred adhesives, acrylic adhesives and rubber-based adhesives can be exemplified. Here, the acrylic adhesive refers to an adhesive containing an acrylic polymer as a base polymer. The same applies to rubber-based adhesives. In addition, the above-mentioned acrylic polymer means a polymer in which 50% by weight or more of the total amount of monomer components constituting the acrylic polymer is an acrylic monomer. In addition, in this specification, the so-called acrylic single system refers to a monomer having at least one (meth)acrylic acid group in one molecule. In addition, the aforementioned (meth)acrylic group includes the meaning of acrylic group and methacrylic group.

可良好地用於此處所揭示之製造方法之黏著劑層之若干例中，包括：(1)含有基礎聚合物及含矽氧烷結構之聚合物之黏著劑層(以下，亦稱為「黏著劑層(1)」)、及(2)由含有基礎聚合物及光硬化劑之光硬化性組合物所形成之黏著劑層(以下，亦稱為「黏著劑層(2)」)。以下，對黏著劑層(1)及黏著劑層(2)進行詳細說明，但此處所揭示之製造方法所使用之黏著片材並不限定於具有該等黏著劑層者。Several examples of the adhesive layer that can be used well in the manufacturing method disclosed here include: (1) An adhesive layer containing a base polymer and a polymer containing a silicone structure (hereinafter, also referred to as "adhesive Agent layer (1)"), and (2) an adhesive layer (hereinafter, also referred to as "adhesive layer (2)") formed of a photocurable composition containing a base polymer and a light curing agent. Hereinafter, the adhesive layer (1) and the adhesive layer (2) will be described in detail, but the adhesive sheet used in the manufacturing method disclosed here is not limited to those having the adhesive layer.

＜含有基礎聚合物A及含矽氧烷結構之聚合物B之黏著劑層＞ 黏著劑層(1)含有基礎聚合物A及含矽氧烷結構之聚合物B，且可顯示出如下性質：於貼合於被黏著體後，於室溫區域(例如20℃～30℃)，於一段時間內黏著力被抑制為較低，藉由老化(可為加熱、經時、該等之組合等)，黏著力大幅地上升。因此，可良好地用於此處所揭示之積層體製造方法。黏著劑層(1)可由含有基礎聚合物A或其前驅物與含矽氧烷結構之聚合物B之黏著劑組合物形成。黏著劑組合物之形態並無特別限制，例如可為水分散型、溶劑型、熱熔型、活性光線硬化型(例如UV硬化型)等各種形態。<Adhesive layer containing base polymer A and polymer B containing silicone structure> The adhesive layer (1) contains a base polymer A and a silicone structure-containing polymer B, and can exhibit the following properties: after being attached to the adherend, at room temperature (for example, 20°C to 30°C) , The adhesive force is suppressed to be low within a period of time, and the adhesive force increases greatly due to aging (which can be heating, time, a combination of these, etc.). Therefore, it can be suitably used for the laminated body manufacturing method disclosed here. The adhesive layer (1) can be formed by an adhesive composition containing a base polymer A or its precursor and a silicone structure-containing polymer B. The form of the adhesive composition is not particularly limited. For example, it can be a water-dispersed type, a solvent type, a hot melt type, an active light curing type (for example, a UV curing type), and various other forms.

(基礎聚合物A) 作為黏著劑層(1)之基礎聚合物A(以下，有時簡稱為「聚合物A」)，可良好地使用丙烯酸系聚合物。若使用丙烯酸系聚合物作為聚合物A，則有容易獲得與聚合物B之良好之相溶性之傾向。聚合物A與聚合物B之相溶性良好使黏著劑層內之聚合物B之移動性提高，藉此可有助於實現兼具局部去除步驟中之低黏著性與黏著力上升處理(例如加熱處理)後之強黏著性的黏著劑層(1)，故而較佳。較佳為黏著劑層(1)之50重量%以上為丙烯酸系聚合物。(Base polymer A) As the base polymer A of the adhesive layer (1) (hereinafter, abbreviated as "polymer A" in some cases), an acrylic polymer can be preferably used. If an acrylic polymer is used as the polymer A, there is a tendency that good compatibility with the polymer B is easily obtained. The good compatibility of polymer A and polymer B improves the mobility of polymer B in the adhesive layer, which can help to achieve both low adhesiveness in the local removal step and adhesion increase treatment (such as heating The strong adhesive layer (1) after treatment) is better. Preferably, 50% by weight or more of the adhesive layer (1) is acrylic polymer.

作為丙烯酸系聚合物，例如可良好地使用構成該丙烯酸系聚合物之單體成分總量中之40重量%以上為(甲基)丙烯酸烷基酯者。作為(甲基)丙烯酸烷基酯，可良好地使用在酯末端具有碳數1～20之(即，C1-20 之)直鏈或支鏈狀之烷基者。就容易取得特性之平衡之方面而言，丙烯酸系聚合物之構成單體成分總量中之(甲基)丙烯酸C1-20 烷基酯之比率例如可為50重量%以上，可為55重量%以上，亦可為60重量%以上。就相同之原因而言，構成單體成分總量中之(甲基)丙烯酸C1-20 烷基酯之比率例如可為99.9重量%以下，可為98重量%以下，亦可為95重量%以下。於若干種態樣中，單體成分總量中之(甲基)丙烯酸C1-20 烷基酯之比率例如可為90重量%以下，可為85重量%以下，亦可為80重量%以下。As the acrylic polymer, for example, 40% by weight or more of the total amount of monomer components constituting the acrylic polymer is alkyl (meth)acrylate. As the (meth)acrylic acid alkyl ester, those having a C 1-20 (that is, C 1-20 ) linear or branched alkyl group at the end of the ester can be suitably used. In terms of easy balance of properties, the ratio of C 1-20 alkyl (meth)acrylate in the total amount of the monomer components of the acrylic polymer may be 50% by weight or more, and may be 55% by weight. % Or more, but also 60% by weight or more. For the same reason, the ratio of (meth)acrylic acid C 1-20 alkyl ester in the total monomer component can be, for example, 99.9% by weight or less, 98% by weight or less, or 95% by weight. the following. In some aspects , the ratio of C 1-20 alkyl (meth)acrylate in the total amount of monomer components may be, for example, 90% by weight or less, 85% by weight or less, or 80% by weight or less .

作為(甲基)丙烯酸C1-20 烷基酯之非限定性具體例，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸異十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。As non-limiting specific examples of C 1-20 alkyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (methyl) ) Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate Ester, isoamyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylate 2 -Ethylhexyl ester, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, ( Undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, isotridecyl (meth)acrylate, ten (meth)acrylate Tetraalkyl ester, pentadecyl (meth)acrylate, cetyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, (meth) ) Isostearyl acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc.

於該等中，較佳為至少使用(甲基)丙烯酸C1-18 烷基酯，更佳為至少使用(甲基)丙烯酸C1-14 烷基酯。於若干種態樣中，丙烯酸系聚合物之構成單體成分可包含選自(甲基)丙烯酸C4-12 烷基酯(較佳為丙烯酸C4-10 烷基酯、例如丙烯酸C6-10 烷基酯)之至少一種。例如較佳為包含丙烯酸正丁酯(BA)及丙烯酸2-乙基己酯(2EHA)之一者或兩者之丙烯酸系聚合物，尤佳為至少包含2EHA之丙烯酸系聚合物。作為可良好地使用之其他(甲基)丙烯酸C1-18 烷基酯之例，可列舉：丙烯酸甲酯、甲基丙烯酸甲酯(MMA)、甲基丙烯酸正丁酯(BMA)、甲基丙烯酸2-乙基己酯(2EHMA)、丙烯酸異硬脂酯(ISTA)等。Among them, it is preferable to use at least C 1-18 alkyl (meth)acrylate, and it is more preferable to use at least C 1-14 alkyl (meth)acrylate. In some aspects, the constituent monomer components of the acrylic polymer may include C 4-12 alkyl (meth)acrylates (preferably C 4-10 alkyl acrylates, such as C 6- acrylates). 10 alkyl ester) at least one kind. For example, it is preferably an acrylic polymer containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA), and particularly preferably an acrylic polymer containing at least 2EHA. Examples of other C 1-18 (meth)acrylate C 1-18 alkyl esters that can be used well include: methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), methyl 2-ethylhexyl acrylate (2EHMA), isostearyl acrylate (ISTA), etc.

丙烯酸系聚合物之構成單體成分亦可包含作為主成分之(甲基)丙烯酸烷基酯並且視需要包含能夠與(甲基)丙烯酸烷基酯共聚之其他單體(共聚性單體)。作為共聚性單體，可良好地使用具有極性基(例如羧基、羥基等)之單體。具有極性基之單體可有助於對丙烯酸系聚合物導入交聯點、或提高丙烯酸系聚合物之凝聚力。共聚性單體可單獨使用一種或組合兩種以上使用。The constituent monomer components of the acrylic polymer may also include an alkyl (meth)acrylate as the main component and, if necessary, other monomers (copolymerizable monomers) copolymerizable with the alkyl (meth)acrylate. As the copolymerizable monomer, a monomer having a polar group (for example, a carboxyl group, a hydroxyl group, etc.) can be used well. Monomers with polar groups can help introduce crosslinking points to the acrylic polymer or increase the cohesive force of the acrylic polymer. The copolymerizable monomer can be used alone or in combination of two or more.

作為共聚性單體之非限定性之具體例，可列舉以下者。 含羧基單體：例如、丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸、異丁烯酸等。 含羥基單體：例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等(甲基)丙烯酸羥基烷基酯；N-(2-羥基乙基)丙烯醯胺(HEAA)等具有羥基與醯胺基之單體等。 含氮單體：例如N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌

Figure 108128671-A0304-12-01
、乙烯基吡
Figure 108128671-A0304-12-01
、乙烯基吡咯、乙烯基咪唑、乙烯基
Figure 108128671-A0304-12-02
唑、乙烯基
Figure 108128671-A0304-12-03
啉、N-乙烯基-3-
Figure 108128671-A0304-12-03
啉酮、N-乙烯基-2-己內醯胺、N-乙烯基-1,3-
Figure 108128671-A0304-12-02
Figure 108128671-A0304-12-01
-2-酮、N-乙烯基-3,5-
Figure 108128671-A0304-12-03
啉二酮、N-丙烯醯基
Figure 108128671-A0304-12-03
啉、N-乙烯基羧醯胺類等。 此外，含氰基單體、乙烯酯單體、芳香族乙烯基單體、含環氧基單體、乙烯醚單體、含磺基單體、含磷酸基單體、含酸酐基單體等。As non-limiting specific examples of the copolymerizable monomer, the following can be cited. Carboxyl group-containing monomers: for example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc. Hydroxyl-containing monomers: for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid ( 4-hydroxymethylcyclohexyl) methyl ester and other (meth) hydroxyalkyl acrylates; N-(2-hydroxyethyl)acrylamide (HEAA) and other monomers having hydroxyl groups and amide groups. Nitrogen-containing monomers: such as N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiper
Figure 108128671-A0304-12-01
Vinylpyridine
Figure 108128671-A0304-12-01
, Vinyl pyrrole, vinyl imidazole, vinyl
Figure 108128671-A0304-12-02
Azole, vinyl
Figure 108128671-A0304-12-03
Morpholine, N-vinyl-3-
Figure 108128671-A0304-12-03
Ketone, N-vinyl-2-caprolactam, N-vinyl-1,3-
Figure 108128671-A0304-12-02
Figure 108128671-A0304-12-01
-2-ketone, N-vinyl-3,5-
Figure 108128671-A0304-12-03
Phylindione, N-acryloyl
Figure 108128671-A0304-12-03
Morpholine, N-vinylcarboxamides, etc. In addition, cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy group-containing monomers, vinyl ether monomers, sulfo group-containing monomers, phosphoric acid group-containing monomers, acid anhydride group-containing monomers, etc. .

於使用此種共聚性單體之情形時，其使用量並無特別限定，通常適宜設為單體成分總量之0.01重量%以上。就更良好地發揮因使用共聚性單體所產生之效果之觀點而言，可將共聚性單體之使用量設為單體成分總量之0.1重量%以上，亦可設為1重量%以上。又，共聚性單體之使用量可設為單體成分總量之50重量%以下，較佳為設為40重量%以下。藉此，可防止黏著劑之凝聚力變得過高，提高常溫(25℃)下之黏著感。In the case of using such a copolymerizable monomer, the amount used is not particularly limited, but it is usually suitably set to 0.01% by weight or more of the total monomer component. From the viewpoint of better exerting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer can be set to 0.1% by weight or more of the total monomer component, or 1% by weight or more . In addition, the amount of the copolymerizable monomer used may be 50% by weight or less of the total amount of monomer components, and preferably 40% by weight or less. This prevents the cohesive force of the adhesive from becoming too high and improves the stickiness at room temperature (25°C).

於若干種態樣中，丙烯酸系聚合物較佳為含有選自由N-乙烯基環狀醯胺及含羥基單體所構成之群中之至少一種單體作為其構成單體成分。In some aspects, the acrylic polymer preferably contains at least one monomer selected from the group consisting of N-vinyl cyclic amides and hydroxyl-containing monomers as its constituent monomer components.

藉由使用N-乙烯基環狀醯胺，可調整黏著劑之凝聚力或極性，提高進行作為使黏著力上升之刺激之加熱後之黏著力(以下，亦稱為「加熱後黏著力」)。作為N-乙烯基環狀醯胺之具體例，可列舉上述含氮單體中具有對應之結構者。作為尤佳之例，可列舉N-乙烯基-2-吡咯啶酮、N-乙烯基-2-己內醯胺。N-乙烯基環狀醯胺之使用量並無特別限制，通常適宜設為丙烯酸系聚合物之構成單體成分總量之0.01重量%以上(較佳為0.1重量%以上，例如0.5重量%以上)。於若干種態樣中，N-乙烯基環狀醯胺之使用量可設為上述單體成分總量之1重量%以上，可設為5重量%以上，可設為8重量%以上，可設為10重量%以上，亦可設為12重量%以上。又，就提高常溫(25℃)下之黏著感或提高低溫下之柔軟性之觀點而言，N-乙烯基環狀醯胺之使用量通常適宜設為上述單體成分總量之40重量%以下，可設為30重量%以下，可設為25重量份以下，可設為20重量%以下，亦可設為18重量%以下。By using N-vinyl cyclic amide, the cohesive force or polarity of the adhesive can be adjusted, and the adhesive force after heating, which is a stimulus to increase the adhesive force, can be improved (hereinafter, also referred to as "adhesion after heating"). As specific examples of N-vinyl cyclic amides, those having a corresponding structure among the aforementioned nitrogen-containing monomers can be cited. Particularly preferable examples include N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam. The amount of N-vinyl cyclic amide used is not particularly limited, and it is generally suitable to be 0.01% by weight or more (preferably 0.1% by weight or more, for example, 0.5% by weight or more) of the total monomer components of the acrylic polymer ). In several aspects, the amount of N-vinyl cyclic amide can be set to 1% by weight or more of the total amount of the above monomer components, can be set to 5% by weight or more, can be set to 8% by weight or more, It is 10 weight% or more, and it can also be 12 weight% or more. In addition, from the viewpoint of improving the stickiness at normal temperature (25°C) or improving the flexibility at low temperature, the amount of N-vinyl cyclic amide used is usually set to 40% by weight of the total amount of the monomer components. Hereinafter, it may be 30 weight% or less, it may be 25 weight% or less, it may be 20 weight% or less, and it may be 18 weight% or less.

藉由使用含羥基單體，可調整黏著劑之凝聚力或極性，可提高加熱後黏著力。又，含羥基單體提供與下述交聯劑(例如異氰酸酯系交聯劑)之反應點，可藉由交聯反應而提高黏著劑之凝聚力。作為含羥基單體之較佳例，可列舉：丙烯酸2-羥基乙酯(HEA)、丙烯酸4-羥基丁酯(4HBA)、N-(2-羥基乙基)丙烯醯胺(HEAA)。含羥基單體之使用量並無特別限制，通常適宜設為丙烯酸系聚合物之構成單體成分總量之0.01重量%以上(較佳為0.1重量%以上，例如0.5重量%以上)。於若干種態樣中，含羥基單體之使用量可設為上述單體成分總量之1重量%以上，可設為5重量%以上，亦可設為10重量%以上。又，就提高常溫(25℃)下之黏著感或提高低溫下之柔軟性之觀點而言，含羥基單體之使用量通常適宜設為上述單體成分總量之40重量%以下，可設為30重量%以下，可設為20重量%以下，亦可設為10重量%以下或5重量%以下。By using hydroxyl-containing monomers, the cohesive force or polarity of the adhesive can be adjusted, and the adhesive force after heating can be improved. In addition, the hydroxyl-containing monomer provides a reaction point with the following cross-linking agent (for example, an isocyanate-based cross-linking agent), and the cohesive force of the adhesive can be improved by the cross-linking reaction. Preferred examples of hydroxyl-containing monomers include 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4HBA), and N-(2-hydroxyethyl)acrylamide (HEAA). The usage amount of the hydroxyl-containing monomer is not particularly limited, and it is usually suitably set to 0.01% by weight or more (preferably 0.1% by weight or more, for example, 0.5% by weight or more) of the total amount of the monomer components of the acrylic polymer. In some aspects, the usage amount of the hydroxyl-containing monomer can be set to 1% by weight or more of the total amount of the monomer components, can be set to 5% by weight or more, or can be set to 10% by weight or more. In addition, from the viewpoint of improving the stickiness at normal temperature (25°C) or improving the flexibility at low temperature, the amount of hydroxyl-containing monomer is usually set to 40% by weight or less of the total amount of the above monomer components. It is 30% by weight or less, may be 20% by weight or less, or may be 10% by weight or less or 5% by weight or less.

於若干種態樣中，作為共聚性單體，可併用N-乙烯基環狀醯胺與含羥基單體。於此情形時，N-乙烯基環狀醯胺與含羥基單體之合計量例如可為丙烯酸系聚合物之構成單體成分總量之0.1重量%以上，可為1重量%以上，可為5重量%以上，亦可為10重量%以上、15重量%以上、20重量%以上或25重量%以上。又，N-乙烯基環狀醯胺與含羥基單體之合計量例如可設為上述單體成分總量之50重量%以下，較佳為設為40重量%以下。In some aspects, as a copolymerizable monomer, N-vinyl cyclic amide and a hydroxyl-containing monomer can be used in combination. In this case, the total amount of the N-vinyl cyclic amide and the hydroxyl-containing monomer can be, for example, 0.1% by weight or more of the total monomer components of the acrylic polymer, 1% by weight or more, or 5% by weight or more, and may also be 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more. In addition, the total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer can be, for example, 50% by weight or less of the total amount of the monomer components, and preferably 40% by weight or less.

於併用N-乙烯基環狀醯胺與含羥基單體之態樣中，N-乙烯基環狀醯胺之使用量(WN )與含羥基單體之使用量(WOH )之關係(重量基準)並無特別限定。WN /WOH 例如可為0.01以上，通常適宜為0.05以上，可為0.1以上，可為0.2以上，可為0.5以上，亦可為0.7以上。又，WN /WOH 例如可為100以下，通常適宜為20以下，可為10以下，可為5以下，可為2以下，可為1.5以下，亦可為1.3以下。In the case where N-vinyl cyclic amide and hydroxyl-containing monomer are used in combination, the relationship between the amount of N-vinyl cyclic amide (W N ) and the amount of hydroxyl-containing monomer (W OH ) ( (Weight basis) is not particularly limited. W N /W OH may be, for example, 0.01 or more, and usually 0.05 or more is suitable, it may be 0.1 or more, it may be 0.2 or more, it may be 0.5 or more, or it may be 0.7 or more. In addition, W N /W OH may be, for example, 100 or less, and usually 20 or less is appropriate, 10 or less, 5 or less, 2 or less, 1.5 or less, or 1.3 or less.

聚合物A之Tg典型而言未達0℃，較佳為未達-10℃，更佳為未達-20℃。含有Tg未達0℃之聚合物A之黏著劑顯示出適度之流動性(例如該黏著劑中所含之聚合物鏈之運動性)，因此，藉由在任意時刻進行加熱處理而容易使黏著力大幅地上升。於若干種態樣中，聚合物A之Tg例如可未達 -30℃，可未達-40℃，可未達-50℃，亦可未達-60℃。聚合物A之Tg之下限並無特別限制。就材料之獲取容易性或提高黏著劑層之凝聚力之觀點而言，通常可良好地採用Tg為-80℃以上之聚合物A。The Tg of polymer A is typically less than 0°C, preferably less than -10°C, and more preferably less than -20°C. Adhesives containing polymer A with a Tg of less than 0°C show moderate fluidity (for example, the mobility of the polymer chains contained in the adhesive). Therefore, it is easy to adhere by heating at any time Power rises sharply. In several aspects, the Tg of polymer A may not reach -30°C, may not reach -40°C, may not reach -50°C, or may not reach -60°C, for example. The lower limit of Tg of polymer A is not particularly limited. From the viewpoint of easy access to materials or improvement of the cohesive force of the adhesive layer, polymer A with a Tg of -80°C or higher can generally be used well.

本說明書中，聚合物之Tg係指文獻或目錄等所記載之標稱值、或基於該聚合物之製備所使用之單體成分之組成根據Fox式所求出之Tg。Fox式係指如以下所示，共聚物之Tg與使構成該共聚物之單體各者進行均聚所獲得之均聚物之玻璃轉移溫度Tgi的關係式。 1/Tg＝Σ(Wi/Tgi) 於上述Fox式中，Tg表示共聚物之玻璃轉移溫度(單位：K)，Wi表示該共聚物中之單體i之重量分率(重量基準之共聚比率)，Tgi表示單體i之均聚物之玻璃轉移溫度(單位：K)。於Tg特定之對象之聚合物為均聚物之情形時，該均聚物之Tg與對象之聚合物之Tg一致。In this specification, the Tg of a polymer refers to the nominal value described in documents or catalogs, or the Tg calculated based on the Fox formula based on the composition of the monomer components used in the preparation of the polymer. The Fox formula refers to the relationship between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer as shown below. 1/Tg=Σ(Wi/Tgi) In the above Fox formula, Tg represents the glass transition temperature of the copolymer (unit: K), Wi represents the weight fraction of monomer i in the copolymer (copolymerization ratio on a weight basis), and Tgi represents the homopolymerization of monomer i The glass transition temperature of the object (unit: K). When the target polymer specified by Tg is a homopolymer, the Tg of the homopolymer is the same as the Tg of the target polymer.

作為用於算出Tg之均聚物之玻璃轉移溫度，設為使用公知資料所記載之值者。具體而言，可列舉「Polymer Handbook」(第3版，John Wiley & Sons, Inc., 1989年)中之數值。關於上述Polymer Handbook中記載有複數種值之單體，採用最高值。As the glass transition temperature of the homopolymer for calculating Tg, use the value described in a known document. Specifically, the values in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) can be cited. For monomers with multiple values described in the above-mentioned Polymer Handbook, the highest value is used.

聚合物A之重量平均分子量(Mw)通常適宜為約5萬以上，但並無特別限定，就獲得顯示出更良好之凝聚性之黏著劑之觀點而言，例如可為10萬以上，可為20萬以上，可為30萬以上，可為50萬以上，亦可為70萬以上。又，聚合物A之Mw通常適宜為約500萬以下。該Mw之聚合物A容易形成顯示出適度之流動性(聚合物鏈之運動性)之黏著劑，因此適於實現黏著力上升比高之黏著片材。於若干種態樣中，聚合物A之Mw可為300萬以下，可為200萬以下，亦可為150萬以下。The weight average molecular weight (Mw) of polymer A is usually about 50,000 or more, but it is not particularly limited. From the viewpoint of obtaining an adhesive showing better cohesiveness, it can be, for example, 100,000 or more. More than 200,000, can be more than 300,000, can be more than 500,000, or more than 700,000. In addition, the Mw of polymer A is usually preferably about 5 million or less. The Mw polymer A is easy to form an adhesive showing moderate fluidity (movement of the polymer chain), so it is suitable for realizing an adhesive sheet with a high increase in adhesive force. In some aspects, the Mw of polymer A can be 3 million or less, 2 million or less, or 1.5 million or less.

於本說明書中，聚合物之Mw可藉由凝膠滲透層析法(GPC)進行聚苯乙烯換算而求出。更具體而言，可依據下述實施例中所記載之方法及條件測定Mw。In this specification, the Mw of the polymer can be calculated by gel permeation chromatography (GPC) and polystyrene conversion. More specifically, Mw can be measured according to the method and conditions described in the following examples.

獲得丙烯酸系聚合物之方法並無特別限定，可適當採用溶液聚合法、乳液聚合法、塊體聚合法、懸濁聚合法、光聚合法等作為丙烯酸系聚合物之合成方法已知之各種聚合方法。The method of obtaining acrylic polymer is not particularly limited, and various polymerization methods known as acrylic polymer synthesis methods, such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization, can be suitably used. .

用於聚合之起始劑可對應於聚合方法而自先前公知之熱起始劑或光起始劑等適當選擇。作為熱起始劑之非限定性之例，可列舉：2,2'-偶氮二異丁腈(AIBN)等偶氮系起始劑、過硫酸鉀等過硫酸鹽、過氧化物系起始劑、氧化還原系起始劑等。作為光起始劑之非限定性之例，可列舉：安息香醚系光起始劑、苯乙酮系光起始劑、α-酮醇系光起始劑、芳香族磺醯氯系光起始劑、光活性肟系光起始劑、安息香系光起始劑、苯偶醯系光起始劑、二苯甲酮系光起始劑、縮酮系光起始劑、9-氧硫

Figure 108128671-A0304-12-04
Figure 108128671-A0304-12-05
系光起始劑、醯基氧化膦系光起始劑等。起始劑可單獨使用一種或組合兩種以上使用。The initiator used for the polymerization can be appropriately selected from previously known thermal initiators or photoinitiators according to the polymerization method. Non-limiting examples of thermal initiators include: 2,2'-azobisisobutyronitrile (AIBN) and other azo-based initiators, potassium persulfate and other persulfates, and peroxide-based Starter, redox system starter, etc. Non-limiting examples of photoinitiators include: benzoin ether-based photoinitiators, acetophenone-based photoinitiators, α-keto alcohol-based photoinitiators, aromatic sulfonyl chloride-based photoinitiators Starter, photoactive oxime-based photoinitiator, benzoin-based photoinitiator, benzophenone-based photoinitiator, benzophenone-based photoinitiator, ketal-based photoinitiator, 9-oxysulfur
Figure 108128671-A0304-12-04
Figure 108128671-A0304-12-05
It is a photoinitiator, phosphine oxide-based photoinitiator, etc. The initiator can be used alone or in combination of two or more.

於若干種態樣中，作為獲得丙烯酸系聚合物之方法，可良好地採用溶液聚合法。作為溶液聚合之溶劑，可使用乙酸乙酯、甲苯等。溶液濃度通常為20～80重量%左右。作為起始劑，可使用偶氮系、過氧化物系等各種公知者。為了調整分子量，亦可使用鏈轉移劑。反應溫度通常可為50～80℃左右，反應時間通常可為1～8小時左右。In several aspects, as a method for obtaining acrylic polymers, a solution polymerization method can be used well. As a solvent for solution polymerization, ethyl acetate, toluene, etc. can be used. The solution concentration is usually about 20 to 80% by weight. As the initiator, various known ones such as azo-based and peroxide-based can be used. In order to adjust the molecular weight, a chain transfer agent may also be used. The reaction temperature can usually be about 50 to 80°C, and the reaction time can usually be about 1 to 8 hours.

於若干種態樣中，丙烯酸系聚合物可以對在如上所述之單體成分中調配起始劑所得之混合物照射紫外線(UV)而使該單體成分之一部分聚合之部分聚合物(丙烯酸系聚合物漿液)之形態，含有於用以形成黏著劑層之黏著劑組合物中。可將含有該丙烯酸系聚合物漿液之黏著劑組合物塗佈於特定之被塗佈體，照射UV而使聚合完成。即，上述丙烯酸系聚合物漿液可作為丙烯酸系聚合物之前驅物理解。黏著劑層(1)例如可使用含有此種丙烯酸系聚合物漿液與聚合物B之黏著劑組合物形成。In several aspects, the acrylic polymer can be irradiated with ultraviolet (UV) to the mixture obtained by blending the initiator in the monomer component as described above to cause a part of the monomer component to polymerize the partial polymer (acrylic The form of polymer slurry) is contained in the adhesive composition used to form the adhesive layer. The adhesive composition containing the acrylic polymer slurry can be applied to a specific coated body and irradiated with UV to complete the polymerization. That is, the aforementioned acrylic polymer slurry can be understood as an acrylic polymer precursor. The adhesive layer (1) can be formed using an adhesive composition containing such an acrylic polymer slurry and polymer B, for example.

(含矽氧烷結構之聚合物B) 含矽氧烷結構之聚合物B(以下，有時簡稱為「聚合物B」)係具有聚有機矽氧烷骨架之單體(以下，亦稱為「單體S1」)與(甲基)丙烯酸系單體之共聚物。聚合物B藉由源自單體S1之聚有機矽氧烷結構之低極性及運動性，可發揮作為有助於抑制初期黏著力及提高黏著力上升比之黏著力上升延遲劑之功能。作為單體S1，並無特別限定，可使用含有聚有機矽氧烷骨架之任意單體。單體S1藉由源自其結構之低極性，於使用前(貼附於被黏著體前)之黏著片材中促進聚合物B偏靠於黏著劑層表面，表現出貼合初期之輕剝離性(低黏著性)。作為單體S1，可良好地使用在單末端具有聚合性反應基之結構者。根據此種單體S1與(甲基)丙烯酸系單體之共聚，形成在側鏈具有聚有機矽氧烷骨架之聚合物B。該結構之聚合物B藉由側鏈之運動性及移動容易性，而容易成為初期黏著力較低且黏著力上升比較高者。(Polymer B with siloxane structure) The silicone structure-containing polymer B (hereinafter, sometimes referred to as "polymer B") is a monomer having a polyorganosiloxane skeleton (hereinafter, also referred to as "monomer S1") and (methyl) Copolymer of acrylic monomers. Due to the low polarity and mobility of the polyorganosiloxane structure derived from the monomer S1, the polymer B can function as an adhesion force increase delay agent that helps suppress the initial adhesion and improve the adhesion increase ratio. The monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used. Monomer S1, due to its low polarity derived from its structure, promotes polymer B to lean on the surface of the adhesive layer in the adhesive sheet before use (before attaching to the adherend), showing light peeling at the initial stage of lamination Sex (low adhesion). As the monomer S1, a structure having a polymerizable reactive group at one end can be used well. According to the copolymerization of the monomer S1 and the (meth)acrylic monomer, a polymer B having a polyorganosiloxane skeleton in the side chain is formed. Due to the mobility and ease of movement of the side chain, the polymer B of this structure tends to have a lower initial adhesion and a higher increase in adhesion.

作為單體S1，例如可使用下述通式(1)或(2)所表示之化合物。更具體而言，作為信越化學工業股份有限公司製造之單末端反應性聚矽氧油，可列舉：X-22-174ASX、X-22-2426、X-22-2475、KF-2012等。單體S1可單獨使用一種或組合兩種以上使用。 [化1]

Figure 02_image001
[化2]
Figure 02_image003
此處，上述通式(1)、(2)中之R3 為氫或甲基，R4 為甲基或一價之有機基，m及n為0以上之整數。As the monomer S1, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as single-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, etc. can be cited. The monomer S1 can be used alone or in combination of two or more. [化1]
Figure 02_image001
[化2]
Figure 02_image003
Here, R 3 in the above general formulas (1) and (2) is hydrogen or methyl, R 4 is methyl or a monovalent organic group, and m and n are integers of 0 or more.

單體S1之官能基當量例如較佳為700 g/mol以上且未達15000 g/mol，更佳為800 g/mol以上且未達10000 g/mol，進而較佳為850 g/mol以上且未達6000 g/mol，尤佳為1500 g/mol以上且未達5000 g/mol。若單體S1之官能基當量未達700 g/mol，則可能有無法充分地抑制初期黏著力之情況。若單體S1之官能基當量為15000 g/mol以上，則可能有黏著力之上升變得不充分之情況。若單體S1之官能基當量為上述範圍內，則容易將黏著劑層內之相溶性(例如與聚合物A之相溶性)或移動性調節為適度之範圍，容易實現以較高之水準兼顧初期之低黏著性與積層體使用時之強黏著性的黏著片材。The functional group equivalent of monomer S1 is, for example, preferably 700 g/mol or more and less than 15000 g/mol, more preferably 800 g/mol or more and less than 10,000 g/mol, and still more preferably 850 g/mol or more and It is less than 6000 g/mol, particularly preferably 1500 g/mol or more and less than 5000 g/mol. If the functional group equivalent of monomer S1 is less than 700 g/mol, there may be cases where the initial adhesion cannot be sufficiently suppressed. If the functional group equivalent of monomer S1 is 15000 g/mol or more, the increase in adhesive force may become insufficient. If the functional group equivalent of monomer S1 is within the above range, it is easy to adjust the compatibility (for example, compatibility with polymer A) or mobility in the adhesive layer to an appropriate range, and it is easy to achieve a high level of compatibility Adhesive sheet with low adhesion in the initial stage and strong adhesion when the laminate is used.

此處，所謂「官能基當量」，意指鍵結於每1個官能基之主骨架(例如聚二甲基矽氧烷)之重量。關於標記單位g/mol，換算成官能基1 mol。單體S1之官能基當量例如可根據基於核磁共振(NMR)之1 H-NMR(質子NMR)之光譜強度而算出。基於1 H-NMR之光譜強度之單體S1之官能基當量(g/mol)之算出可基於有關1 H-NMR光譜解析之一般結構解析方法，視需要參照日本專利第5951153號公報之記載而進行。Here, the "functional group equivalent" means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to one functional group. Regarding the labeling unit g/mol, it is converted to 1 mol of the functional group. The functional group equivalent of monomer S1 can be calculated based on 1 H-NMR (proton NMR) spectral intensity based on nuclear magnetic resonance (NMR), for example. The calculation of the functional group equivalent (g/mol) of monomer S1 based on 1 H-NMR spectrum intensity can be based on the general structure analysis method related to 1 H-NMR spectrum analysis, and if necessary, refer to the description of Japanese Patent No. 5951153 get on.

再者，於使用官能基當量不同之兩種以上之單體作為單體S1之情形時，作為單體S1之官能基當量，可使用算術平均值。即，包含官能基當量不同之n種單體(單體S11 、單體S12 ……單體S1n )的單體S1之官能基當量可藉由下述式進行計算。 單體S1之官能基當量(g/mol)＝(單體S11 之官能基當量×單體S11 之調配量＋單體S12 之官能基當量×單體S12 之調配量＋……＋單體S1n 之官能基當量×單體S1n 之調配量)/(單體S11 之調配量＋單體S12 之調配量＋……＋單體S1n 之調配量)Furthermore, when two or more monomers with different functional group equivalents are used as the monomer S1, the arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of monomer S1 including n types of monomers (monomer S1 1 , monomer S1 2 ... monomer S1 n ) having different functional group equivalents can be calculated by the following formula. S1 functional group equivalent of the monomer (g / mol) = functionality (S1 monomer. 1 × monomers of group equivalent amount of formulation S1. 1 S1 2 + monomer having a functional group equivalent of the amount of formulation S1 × monomers of 2 + ...... the monomer S1 + n × functional group equivalent of the monomer blending amount of n-S1) / (S1 formulation. 1 the formulation amount of the monomers of the monomer S1 + 2 + ...... + the amount of the monomer formulation of n-S1)

單體S1之含量相對於用以製備聚合物B之全部單體成分，例如可為5重量%以上，就更良好地發揮作為黏著力上升延遲劑之效果之觀點而言，較佳為設為10重量%以上，可設為15重量%以上，亦可設為20重量%以上。又，就聚合反應性或相溶性之觀點而言，單體S1之含量相對於用以製備聚合物B之全部單體成分，適宜設為60重量%以下，可設為50重量%以下，可設為40重量%以下，亦可設為30重量%以下。若單體S1之含量少於5重量%，則可能有無法充分地抑制初期黏著力之情況。若單體S1之含量多於60重量%，則可能有黏著力之上升變得不充分之情況。The content of the monomer S1 relative to the total monomer components used to prepare the polymer B may be, for example, 5% by weight or more. From the viewpoint of better exhibiting the effect as a retarder for increasing the adhesion, it is preferably set as 10% by weight or more, may be 15% by weight or more, or 20% by weight or more. In addition, from the viewpoint of polymerization reactivity or compatibility, the content of the monomer S1 relative to the total monomer components used to prepare the polymer B is suitably set to 60% by weight or less, and can be set to 50% by weight or less. The content is 40% by weight or less, or 30% by weight or less. If the content of the monomer S1 is less than 5% by weight, there may be cases where the initial adhesion cannot be sufficiently suppressed. If the content of the monomer S1 is more than 60% by weight, the increase in adhesion may become insufficient.

聚合物B之製備所使用之單體成分除了含有單體S1以外，亦含有能夠與單體S1共聚之(甲基)丙烯酸系單體。藉由使一種或兩種以上之(甲基)丙烯酸系單體與單體S1進行共聚，可良好地調節黏著劑層內之聚合物B之移動性。使單體S1與(甲基)丙烯酸系單體共聚亦可有助於改善聚合物B與聚合物A(例如丙烯酸系聚合物)之相溶性。The monomer component used in the preparation of the polymer B contains not only the monomer S1 but also a (meth)acrylic monomer which can be copolymerized with the monomer S1. By copolymerizing one or more (meth)acrylic monomers with monomer S1, the mobility of polymer B in the adhesive layer can be well adjusted. The copolymerization of monomer S1 and (meth)acrylic monomers can also help to improve the compatibility of polymer B and polymer A (for example, acrylic polymer).

作為(甲基)丙烯酸系單體，例如可列舉(甲基)丙烯酸烷基酯。例如可使用作為於聚合物A為丙烯酸系聚合物之情形時可使用之(甲基)丙烯酸烷基酯於上文中例示之單體之一種或兩種以上作為聚合物B之共聚成分。於若干種態樣中，聚合物B可含有(甲基)丙烯酸C4-12 烷基酯(較佳為(甲基)丙烯酸C4-10 烷基酯，例如(甲基)丙烯酸C6-10 烷基酯)之至少一種作為單體單元。於其他若干種態樣中，聚合物B可含有甲基丙烯酸C1-18 烷基酯(較佳為甲基丙烯酸C1-14 烷基酯，例如甲基丙烯酸C1-10 烷基酯)之至少一種作為單體單元。構成聚合物B之單體單元例如可含有選自MMA、BMA及2EHMA之一種或兩種以上。As a (meth)acrylic-type monomer, the alkyl (meth)acrylate is mentioned, for example. For example, one or two or more of the monomers exemplified above as the alkyl (meth)acrylate that can be used when the polymer A is an acrylic polymer can be used as the copolymerization component of the polymer B. In several aspects, polymer B may contain (meth)acrylate C 4-12 alkyl ester (preferably (meth)acrylate C 4-10 alkyl ester, for example (meth)acrylate C 6- 10 alkyl ester) as a monomer unit. In several other aspects, polymer B may contain C 1-18 alkyl methacrylate (preferably C 1-14 alkyl methacrylate, such as C 1-10 alkyl methacrylate) At least one of them is used as a monomer unit. The monomer unit constituting the polymer B may contain, for example, one or two or more selected from MMA, BMA, and 2EHMA.

作為上述(甲基)丙烯酸系單體之其他例，可列舉具有脂環式烴基之(甲基)丙烯酸酯。例如可使用(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異

Figure 108128671-A0304-12-06
酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸1-金剛烷基酯等。於若干種態樣中，聚合物B可含有選自甲基丙烯酸二環戊酯、甲基丙烯酸異
Figure 108128671-A0304-12-06
酯及甲基丙烯酸環己酯之至少一種作為單體單元。As another example of the said (meth)acrylic-type monomer, the (meth)acrylate which has an alicyclic hydrocarbon group is mentioned. For example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isopropyl (meth)acrylate can be used
Figure 108128671-A0304-12-06
Ester, dicyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc. In several aspects, polymer B may contain isopropyl methacrylate selected from dicyclopentyl methacrylate,
Figure 108128671-A0304-12-06
At least one of ester and cyclohexyl methacrylate is used as a monomer unit.

上述(甲基)丙烯酸烷基酯及上述具有脂環式烴基之(甲基)丙烯酸酯之使用量相對於用以製備聚合物B之全部單體成分，例如可為10重量%以上且95重量%以下，可為20重量%以上且95重量%以下，亦可為30重量%以上且90重量%以下、40重量%以上且90重量%以下、或50重量%以上且85重量%以下。The usage amount of the above-mentioned alkyl (meth)acrylate and the above-mentioned (meth)acrylate having alicyclic hydrocarbon group can be, for example, 10% by weight or more and 95% by weight relative to all monomer components used to prepare polymer B % Or less may be 20% by weight or more and 95% by weight or less, or 30% by weight or more and 90% by weight or less, 40% by weight or more and 90% by weight or less, or 50% by weight or more and 85% by weight or less.

作為構成聚合物B之單體單元中可與單體S1一起含有之單體之其他例，可列舉作為聚合物A為丙烯酸系聚合物之情形時可使用之單體於上文中例示之各種共聚性單體。As other examples of the monomers that can be contained together with the monomer S1 in the monomer units constituting the polymer B, the various copolymerizations exemplified above are the monomers that can be used when the polymer A is an acrylic polymer. Sexual monomer.

於若干種態樣中，藉由使與聚合物B中所含之單體單元共通之單體單元亦含有於聚合物A中，可改善黏著劑層內之聚合物B之移動性，提高黏著力上升比。共通之單體單元為佔據構成聚合物B之全部單體單元之5重量%以上的成分時有效，較佳為占10重量%以上(更佳為20重量%以上，例如30重量%以上)之成分。上述共通之單體單元於構成聚合物A之全部單體單元中所占之比率例如可為1重量%以上，較佳為3重量%以上，更佳為5重量%以上，亦可為7重量%以上。若共通之單體單元於構成聚合物A之全部單體單元中所占之比率變高，則有更良好地發揮改善相溶性之效果之傾向。又，考慮與其他特性之平衡性，共通之單體單元於構成聚合物A之全部單體單元中所占之比率可為50重量%以下，可為30重量%以下，亦可為15重量%以下。作為可良好地用作共通之單體單元之單體之非限定性之例，可列舉：MMA、BMA、2EHMA、丙烯酸甲酯(MA)、BA、2EHA、(甲基)丙烯酸環己酯、(甲基)丙烯酸異

Figure 108128671-A0304-12-06
酯、(甲基)丙烯酸二環戊酯等。In some aspects, by making the monomer unit common to the monomer unit contained in the polymer B also contained in the polymer A, the mobility of the polymer B in the adhesive layer can be improved, and the adhesion can be improved. Force rise ratio. The common monomer unit is effective when it occupies 5% by weight or more of all monomer units constituting the polymer B, and it is preferably 10% by weight or more (more preferably 20% by weight or more, for example, 30% by weight or more). ingredient. The ratio of the above-mentioned common monomer units in all the monomer units constituting the polymer A can be, for example, 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, or 7% by weight %the above. If the ratio of the common monomer unit to all the monomer units constituting the polymer A becomes higher, the effect of improving the compatibility will tend to be better exhibited. In addition, considering the balance with other characteristics, the ratio of the common monomer unit in all the monomer units constituting the polymer A can be 50% by weight or less, 30% by weight or less, or 15% by weight the following. Non-limiting examples of monomers that can be used as common monomer units well include: MMA, BMA, 2EHMA, methyl acrylate (MA), BA, 2EHA, cyclohexyl (meth)acrylate, (Meth) acrylic iso
Figure 108128671-A0304-12-06
Esters, dicyclopentyl (meth)acrylate, etc.

聚合物B之Mw並無特別限定。聚合物B之Mw例如可為1000以上，亦可為5000以上。就提高由加熱所產生之黏著力上升性之觀點而言，於若干種態樣中，聚合物B之Mw例如可為10000以上，可為12000以上，可為15000以上，可為17000以上，亦可為20000以上。又，聚合物B之Mw例如可為500000以下，亦可為350000以下。於局部去除步驟中，就容易將第二區域自被黏著體剝離之觀點而言，於若干種態樣中，聚合物B之Mw例如可為100000以下，可為70000以下，可為50000以下，可未達50000，可未達40000，可未達35000，可為30000以下，可為28000以下，亦可為25000以下。若聚合物B之Mw為上述任一上限值及下限值之範圍內，則容易將黏著劑層內之相溶性或移動性調節為適度之範圍，容易以較高之水準同時實現局部去除步驟中之低黏著性與積層體使用時之強黏著性。The Mw of polymer B is not particularly limited. The Mw of the polymer B may be 1000 or more, or 5000 or more, for example. From the viewpoint of improving the increase in adhesion caused by heating, in some aspects, the Mw of polymer B can be, for example, 10,000 or more, 12,000 or more, 15,000 or more, 17,000 or more, or It can be more than 20,000. In addition, the Mw of the polymer B may be 500,000 or less, or 350,000 or less, for example. In the partial removal step, from the viewpoint of easy peeling of the second area from the adherend, in some aspects, the Mw of polymer B can be, for example, 100,000 or less, 70,000 or less, or 50,000 or less, It can be less than 50,000, can be less than 40,000, can be less than 35,000, can be less than 30,000, can be less than 28,000, or less than 25,000. If the Mw of polymer B is within any of the above upper and lower limits, it is easy to adjust the compatibility or mobility in the adhesive layer to a moderate range, and it is easy to achieve local removal at a higher level at the same time Low adhesion in the process and strong adhesion when the laminate is used.

聚合物B例如可藉由利用溶液聚合法、乳液聚合法、塊體聚合法、懸濁聚合法、光聚合法等公知方法使上述單體聚合而製作。The polymer B can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method.

為了調整聚合物B之分子量，可使用鏈轉移劑。作為所使用之鏈轉移劑之例，可列舉：辛基硫醇、月桂基硫醇、第三壬基硫醇、第三(十二烷基)硫醇、巰基乙醇、α-硫甘油等具有巰基之化合物；硫代乙醇酸；硫代乙醇酸甲酯、硫代乙醇酸乙酯、硫代乙醇酸丙酯、硫代乙醇酸丁酯、硫代乙醇酸第三丁酯、硫代乙醇酸2-乙基己酯、硫代乙醇酸辛酯、硫代乙醇酸異辛酯、硫代乙醇酸癸酯、硫代乙醇酸十二烷基酯、乙二醇之硫代乙醇酸酯、新戊二醇之硫代乙醇酸酯、季戊四醇之硫代乙醇酸酯等硫代乙醇酸酯類；α-甲基苯乙烯二聚物等。In order to adjust the molecular weight of polymer B, a chain transfer agent can be used. Examples of chain transfer agents used include: octyl mercaptan, lauryl mercaptan, tertiary nonyl mercaptan, tertiary (dodecyl) mercaptan, mercaptoethanol, α-thioglycerol, etc. Sulfhydryl compounds; thioglycolic acid; methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, tert-butyl thioglycolic acid, thioglycolic acid 2-ethylhexyl ester, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, lauryl thioglycolate, thioglycolate of ethylene glycol, neopentyl Thioglycolic acid esters such as glycol thioglycolate and pentaerythritol thioglycolate; α-methylstyrene dimer, etc.

作為鏈轉移劑之使用量，並無特別限制，通常相對於單體100重量份，適宜設為0.05重量份～20重量份，較佳為0.1重量份～15重量份，進而較佳為0.2重量份～10重量份。藉由如此調整鏈轉移劑之使用量，可獲得較佳之分子量之聚合物B。鏈轉移劑可單獨使用一種或組合兩種以上使用。The amount of chain transfer agent used is not particularly limited, but it is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.2 part by weight relative to 100 parts by weight of the monomer. Parts ~ 10 parts by weight. By adjusting the amount of chain transfer agent used in this way, polymer B with a better molecular weight can be obtained. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types.

聚合物B之使用量相對於聚合物A之使用量100重量份，例如可設為0.1重量份以上，就獲得更高之效果之觀點而言，可設為0.3重量份以上，可設為0.4重量份以上，可設為0.5重量份以上，亦可設為1重量份以上或2重量份以上，但並無特別限定。又，就避免凝聚力之過度之降低之觀點而言，聚合物B之使用量相對於100重量份聚合物A例如可為75重量份以下，可為50重量份以下，可為20重量份以下，可為10重量份以下，可為8重量份以下，亦可為5重量份以下。The usage amount of polymer B relative to 100 parts by weight of the usage amount of polymer A can be set to, for example, 0.1 parts by weight or more. From the viewpoint of obtaining higher effects, it can be set to 0.3 parts by weight or more, or 0.4 parts by weight. Part by weight or more may be 0.5 part by weight or more, or may be 1 part by weight or more or 2 parts by weight or more, but it is not particularly limited. In addition, from the viewpoint of avoiding excessive reduction in cohesive force, the amount of polymer B used relative to 100 parts by weight of polymer A may be 75 parts by weight or less, 50 parts by weight or less, or 20 parts by weight or less. It may be 10 parts by weight or less, 8 parts by weight or less, or 5 parts by weight or less.

黏著劑層可於不會大幅地損及藉由此處所揭示之技術所獲得之效果之範圍內，視需要含有聚合物A及聚合物B以外之聚合物(任意聚合物)。此種任意聚合物之使用量通常適宜設為黏著劑層中所含之全部聚合物成分之20重量%以下。於若干種態樣中，上述任意聚合物之使用量可為上述全部聚合物成分之5重量%以下，亦可為1重量%以下。亦可為實質上不含聚合物A及聚合物B以外之聚合物之黏著劑層。The adhesive layer may contain polymers (arbitrary polymers) other than polymer A and polymer B as needed within a range that does not greatly impair the effects obtained by the technology disclosed herein. The usage amount of this arbitrary polymer is usually suitably set to 20% by weight or less of all polymer components contained in the adhesive layer. In some aspects, the usage amount of any of the above-mentioned polymers may be 5% by weight or less of the total polymer components, or may be 1% by weight or less. It may also be an adhesive layer substantially free of polymers other than polymer A and polymer B.

(交聯劑) 於黏著劑層中，可以調整凝聚力等為目的視需要使用交聯劑。作為交聯劑，可使用黏著劑之領域中公知之交聯劑，例如可列舉：異氰酸酯系交聯劑、環氧系交聯劑、

Figure 108128671-A0304-12-02
唑啉系交聯劑、氮丙啶系交聯劑、碳二醯亞胺系交聯劑、金屬螯合物系交聯劑等。尤佳為異氰酸酯系交聯劑、環氧系交聯劑、金屬螯合物系交聯劑。交聯劑可單獨使用一種或組合兩種以上使用。此處所揭示之技術可以至少使用異氰酸酯系交聯劑作為交聯劑之態樣良好地實施。(Crosslinking agent) In the adhesive layer, a crosslinking agent can be used as needed for the purpose of adjusting cohesive force. As the crosslinking agent, a crosslinking agent known in the field of adhesives can be used, for example, isocyanate-based crosslinking agents, epoxy-based crosslinking agents,
Figure 108128671-A0304-12-02
Oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, metal chelate-based cross-linking agents, etc. Particularly preferred are isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types. The technique disclosed here can be implemented satisfactorily in a state where at least an isocyanate-based crosslinking agent is used as a crosslinking agent.

作為異氰酸酯系交聯劑之例，可列舉：伸丁基二異氰酸酯、六亞甲基二異氰酸酯等低級脂肪族多異氰酸酯類；伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯類；2,4-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族異氰酸酯類；三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物(例如Tosoh製造之「Coronate L」)、三羥甲基丙烷/六亞甲基二異氰酸酯三聚物加成物(例如Tosoh製造之「Coronate HL」)、苯二甲基二異氰酸酯之三羥甲基丙烷加成物(例如三井化學製造之「Takenate D110N」，六亞甲基二異氰酸酯之異氰尿酸酯體(例如Tosoh製造之「Coronate HX」)等異氰酸酯加成物等。Examples of isocyanate-based crosslinking agents include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, etc. Alicyclic isocyanates such as isocyanates; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/toluene diisocyanate three Polymer adducts (e.g. "Coronate L" manufactured by Tosoh), trimethylolpropane/hexamethylene diisocyanate trimer adducts (e.g. "Coronate HL" manufactured by Tosoh), xylylene diisocyanate Trimethylolpropane adduct of isocyanate (for example, "Takenate D110N" manufactured by Mitsui Chemicals, isocyanurate of hexamethylene diisocyanate (for example, "Coronate HX" manufactured by Tosoh)) and other isocyanate adducts, etc. .

作為環氧系交聯劑，可列舉：雙酚A、表氯醇型環氧系樹脂、伸乙基縮水甘油醚、聚乙二醇二縮水甘油醚、甘油二縮水甘油醚、甘油三縮水甘油醚、1,6-己二醇縮水甘油醚、三羥甲基丙烷三縮水甘油醚、二縮水甘油基苯胺、二胺縮水甘油胺、N,N,N',N'-四縮水甘油基間苯二甲胺及1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷等。Examples of epoxy crosslinking agents include: bisphenol A, epichlorohydrin type epoxy resins, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl Ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl Xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, etc.

使用交聯劑之情形時之使用量並無特別限定，例如相對於100重量份聚合物A可設為超過0重量份之量。於若干種態樣中，交聯劑之使用量相對於100重量份聚合物A，例如可為0.01重量份以上，可為0.05重量份以上，亦可為0.1重量份以上、0.5重量份以上、1重量份以上、1.5重量份以上或2重量份以上。藉由增大交聯劑之使用量，有獲得更高之凝聚力之傾向。另一方面，就避免因過度之凝聚力提高所致之黏性降低之觀點而言，交聯劑之使用量相對於100重量份聚合物A，通常適宜設為15重量份以下，可設為10重量份以下，亦可設為5重量份以下。交聯劑之使用量不過多就利用黏著劑之流動性而更良好地表現出聚合物B之使用效果之觀點而言亦可能變得有利。The amount of use in the case of using a crosslinking agent is not particularly limited. For example, it can be set to an amount exceeding 0 parts by weight relative to 100 parts by weight of polymer A. In some aspects, the amount of crosslinking agent used relative to 100 parts by weight of polymer A may be, for example, 0.01 parts by weight or more, 0.05 parts by weight or more, or 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more. By increasing the amount of crosslinking agent used, there is a tendency to obtain higher cohesion. On the other hand, from the viewpoint of avoiding the decrease in viscosity due to excessive cohesion increase, the amount of crosslinking agent used relative to 100 parts by weight of polymer A is usually preferably set to 15 parts by weight or less, and can be set to 10 Parts by weight or less may also be 5 parts by weight or less. If the amount of the crosslinking agent used is not too large, it may become advantageous from the viewpoint of using the fluidity of the adhesive to better show the effect of the polymer B.

為了更有效地進行交聯反應，亦可使用交聯觸媒。作為交聯觸媒，可例示：鈦酸四正丁酯、鈦酸四異丙酯、乙醯丙酮鐵、氧化丁基錫、二月桂酸二辛基錫等金屬系交聯觸媒等。其中，較佳為二月桂酸二辛基錫等錫系交聯觸媒。交聯觸媒之使用量並無特別限制，例如相對於100重量份聚合物A可設為約0.0001重量份～1重量份(典型而言為0.05重量份以下)。In order to perform the cross-linking reaction more efficiently, a cross-linking catalyst can also be used. Examples of the crosslinking catalyst include metal crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, iron acetone acetone, butyl tin oxide, and dioctyl tin dilaurate. Among them, tin-based crosslinking catalysts such as dioctyltin dilaurate are preferred. The amount of the crosslinking catalyst used is not particularly limited. For example, it can be about 0.0001 part by weight to 1 part by weight (typically 0.05 part by weight or less) relative to 100 parts by weight of polymer A.

於黏著劑層中可視需要使用多官能性單體。多官能性單體藉由代替如上所述之交聯劑、或與該交聯劑組合使用，可有助於實現凝聚力之調整等目的。例如於由光硬化型黏著劑組合物所形成之黏著劑層中，可良好地使用多官能性單體。 作為多官能性單體，例如可列舉：乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,12-十二烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯、二乙烯苯、環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸胺基甲酸酯、丁二醇(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯等。其中，可良好地使用三羥甲基丙烷三(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯。多官能性單體可單獨使用一種或組合兩種以上使用。A multifunctional monomer may be used in the adhesive layer as needed. The multifunctional monomer can be used in place of the above-mentioned crosslinking agent or in combination with the crosslinking agent to help achieve the purpose of adjusting cohesive force. For example, in an adhesive layer formed of a light-curable adhesive composition, a polyfunctional monomer can be used well. Examples of multifunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. Acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate ) Acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, four Hydroxymethylmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, Butylene glycol (meth)acrylate, hexanediol di(meth)acrylate, etc. Among them, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be used favorably. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

多官能性單體之使用量根據其分子量或官能基數等而不同，通常相對於100重量份聚合物A適宜設為0.01重量份～3.0重量份左右之範圍。於若干種態樣中，多官能性單體之使用量相對於100重量份聚合物A，例如可為0.02重量份以上，亦可為0.03重量份以上。藉由增大多官能性單體之使用量，有獲得更高之凝聚力之傾向。另一方面，就避免因過度之凝聚力提高所致之黏性之降低之觀點而言，多官能性單體之使用量相對於100重量份聚合物A可為2.0重量份以下，可為1.0重量份以下，亦可為0.5重量份以下。多官能性單體之使用量不過多就利用黏著劑之流動性而更良好地表現聚合物B之使用效果之觀點而言可能變得有利。The amount of the polyfunctional monomer used varies depending on its molecular weight, the number of functional groups, etc., and it is usually appropriate to set it to a range of about 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polymer A. In some aspects, the amount of the polyfunctional monomer used relative to 100 parts by weight of the polymer A may be, for example, 0.02 parts by weight or more, or 0.03 parts by weight or more. By increasing the amount of polyfunctional monomers used, there is a tendency to obtain higher cohesion. On the other hand, from the viewpoint of avoiding the decrease in viscosity due to excessive cohesive force increase, the amount of polyfunctional monomer used can be 2.0 parts by weight or less, or 1.0 parts by weight, relative to 100 parts by weight of polymer A. Parts or less, and may be 0.5 parts by weight or less. If the amount of the polyfunctional monomer used is not too large, it may become advantageous from the viewpoint of using the fluidity of the adhesive to better express the use effect of the polymer B.

(黏著賦予樹脂) 黏著劑層中可視需要含有黏著賦予樹脂。作為黏著賦予樹脂，並無特別限制，例如可列舉：松香系黏著賦予樹脂、萜烯系黏著賦予樹脂、酚系黏著賦予樹脂、烴系黏著賦予樹脂、酮系黏著賦予樹脂、聚醯胺系黏著賦予樹脂、環氧系黏著賦予樹脂、彈性體系黏著賦予樹脂等。黏著賦予樹脂可單獨使用一種或組合兩種以上使用。(Adhesion imparting resin) The adhesive layer may optionally contain an adhesion-imparting resin. There are no particular limitations on the adhesion-imparting resin. Examples include rosin-based adhesion-imparting resins, terpene-based adhesion-imparting resins, phenol-based adhesion-imparting resins, hydrocarbon-based adhesion-imparting resins, ketone-based adhesion-imparting resins, and polyamide-based adhesion-imparting resins. Adhesive resin, epoxy adhesive resin, elastic system adhesive resin, etc. The adhesion imparting resin can be used alone or in combination of two or more.

於使黏著劑層含有黏著賦予樹脂之態樣中，該黏著賦予樹脂之含量並無特別限定，可以視目的或用途發揮適當之黏著性能之方式設定。黏著賦予樹脂相對於100重量份聚合物A之含量(於含有兩種以上之黏著賦予樹脂之情形時為該等之合計量)例如可設為5～500重量份左右。再者，此處所揭示之技術亦可以黏著賦予樹脂之含量相對於100重量份聚合物A未達5重量份、未達2重量份或未達1重量份之態樣、或者黏著劑層實質上不含黏著賦予樹脂之態樣良好地實施。In the case where the adhesive layer contains the adhesion-imparting resin, the content of the adhesion-imparting resin is not particularly limited, and can be set in a manner that exerts an appropriate adhesion performance depending on the purpose or application. The content of the adhesion-imparting resin relative to 100 parts by weight of the polymer A (when two or more kinds of adhesion-imparting resins are contained, the total amount thereof) can be set at about 5 to 500 parts by weight, for example. Furthermore, the technology disclosed here can also be used in a state where the content of the adhesion-imparting resin is less than 5 parts by weight, less than 2 parts by weight, or less than 1 part by weight relative to 100 parts by weight of polymer A, or the adhesive layer is substantially It is implemented well without the adhesion imparting resin.

作為黏著賦予樹脂，可良好地使用軟化點(軟化溫度)為約80℃以上(較佳為約100℃以上、例如約120℃以上)者。根據具有上述下限值以上之軟化點之黏著賦予樹脂，存在有效地改善初期低黏著性及積層體使用時之強黏著性的傾向。軟化點之上限並無特別限制，例如可為約200℃以下(典型而言180℃以下)。黏著賦予樹脂之軟化點可基於JIS K2207所規定之軟化點試驗方法(環球法)進行測定。As the adhesion-imparting resin, those having a softening point (softening temperature) of about 80°C or higher (preferably about 100°C or higher, for example, about 120°C or higher) can be used well. According to the adhesion-imparting resin having a softening point above the lower limit, there is a tendency to effectively improve the initial low adhesion and strong adhesion when the laminate is used. The upper limit of the softening point is not particularly limited, and may be, for example, about 200°C or less (typically 180°C or less). The softening point of the adhesion-imparting resin can be measured based on the softening point test method (ring and ball method) specified in JIS K2207.

(黏著劑層之形成) 黏著劑層(1)可為黏著劑組合物之硬化層。即，該黏著劑層(1)可藉由將水分散型、溶劑型、光硬化型、熱熔型等之黏著劑組合物塗佈於適當之表面後適當實施硬化處理而形成。於進行兩種以上之硬化處理(乾燥、交聯、聚合、冷卻等)之情形時，該等可同時進行、或以多階段進行。於使用單體成分之部分聚合物(丙烯酸系聚合物漿液)之黏著劑組合物中，典型而言，作為上述硬化處理，係進行最終之共聚反應。即，將部分聚合物供於進一步之共聚反應而形成完全聚合物。例如若為光硬化性之黏著劑組合物，則實施光照射。亦可視需要實施交聯、乾燥等硬化處理。例如於必須以光硬化性黏著劑組合物進行乾燥之情形時，於乾燥後進行光硬化即可。於使用完全聚合物之黏著劑組合物中，典型而言，作為上述硬化處理，視需要實施乾燥(加熱乾燥)、交聯等處理。(Formation of Adhesive Layer) The adhesive layer (1) can be a hardened layer of the adhesive composition. That is, the adhesive layer (1) can be formed by applying an adhesive composition such as a water-dispersed, solvent-based, light-curing type, hot-melt type, etc. on an appropriate surface and then appropriately hardening. When two or more hardening treatments (drying, cross-linking, polymerization, cooling, etc.) are carried out, these can be carried out simultaneously or in multiple stages. In the adhesive composition using the partial polymer (acrylic polymer slurry) of the monomer component, typically, the final copolymerization reaction is performed as the above-mentioned hardening treatment. That is, part of the polymer is subjected to further copolymerization to form a complete polymer. For example, if it is a photocurable adhesive composition, light irradiation is performed. If necessary, cross-linking, drying and other hardening treatments can also be implemented. For example, when it is necessary to dry with a light-curable adhesive composition, light-curing may be performed after drying. In the adhesive composition using a complete polymer, typically, as the above-mentioned hardening treatment, treatments such as drying (heat drying) and crosslinking are performed as necessary.

黏著劑組合物之塗佈例如可使用凹版輥式塗佈機、逆輥塗佈機、接觸輥塗佈機、浸漬輥塗機、棒式塗佈機、刮刀塗佈機、噴霧塗佈機等慣用之塗佈機實施。用於下述黏著劑層(2)之形成之黏著劑組合物及其他黏著劑組合物之塗佈亦可藉由相同之方式實施。For coating the adhesive composition, for example, a gravure roll coater, a reverse roll coater, a touch roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, etc. can be used Implementation of conventional coating machine. The adhesive composition used for the formation of the following adhesive layer (2) and the coating of other adhesive compositions can also be implemented in the same way.

＜由含有基礎聚合物P及光硬化劑之光硬化性組合物所形成之黏著劑層＞ 黏著劑層(2)含有基礎聚合物P及光硬化劑，顯示出藉由活性光線(例如UV)之照射而硬化從而黏著力提高之性質。可利用該性質，以如下態樣良好地用於此處所揭示之積層體製造方法之實施，即，例如以光硬化前之黏著力成為2 N/25 mm以下之方式構成，於該光硬化前進行貼附步驟、切割步驟及局部去除步驟，繼而進行光硬化而使黏著力上升(典型而言，上升至5 N/25 mm以上)。就提高利用活性光線照射之硬化效率之觀點而言，構成黏著劑層(2)之黏著劑組合物(光硬化性組合物)較佳為含有光起始劑。就抑制於使光硬化前之黏著劑層變硬、於局部去除步驟中將第二區域之黏著片材剝離去除時黏著劑殘留於被黏著體上之現象、即糊劑殘留現象之觀點而言，較佳為對基礎聚合物P導入交聯結構。<Adhesive layer formed from photocurable composition containing base polymer P and photocuring agent> The adhesive layer (2) contains a base polymer P and a light hardener, and exhibits the property of hardening by irradiation of active light (such as UV) to increase the adhesive force. This property can be used for the implementation of the laminated body manufacturing method disclosed here in such a way that, for example, the adhesive force before light curing becomes 2 N/25 mm or less, and before the light curing The attaching step, the cutting step, and the partial removal step are performed, and then the photohardening is performed to increase the adhesive force (typically, to 5 N/25 mm or more). From the viewpoint of improving the curing efficiency by active light irradiation, the adhesive composition (photocurable composition) constituting the adhesive layer (2) preferably contains a photoinitiator. From the viewpoint of suppressing the hardening of the adhesive layer before photocuring, the phenomenon that the adhesive remains on the adherend when the adhesive sheet of the second area is peeled off in the partial removal step, that is, the paste residue phenomenon It is preferable to introduce a cross-linked structure to the base polymer P.

(基礎聚合物P) 作為黏著劑層(2)之基礎聚合物P(以下，有時簡稱為「聚合物P」)，就光學透明性等觀點而言，可良好地使用丙烯酸系聚合物。例如較佳為黏著劑層(2)之50重量%以上為丙烯酸系聚合物。作為丙烯酸系聚合物，可良好地使用其構成單體成分總量中之40重量%以上為與上述聚合物A相同之(甲基)丙烯酸烷基酯。(Base polymer P) As the base polymer P (hereinafter, abbreviated as "polymer P") of the adhesive layer (2), an acrylic polymer can be used satisfactorily from the viewpoint of optical transparency and the like. For example, it is preferable that 50% by weight or more of the adhesive layer (2) is acrylic polymer. As the acrylic polymer, 40% by weight or more of the total amount of constituent monomer components is the same alkyl (meth)acrylate as the polymer A described above.

丙烯酸系聚合物較佳為含有具有能夠進行交聯之官能基之單體成分作為共聚成分。作為具有能夠進行交聯之官能基之單體，可列舉含羥基單體或含羧基單體。作為含羥基單體及含羧基單體之例，可列舉與作為黏著劑層(1)中所含之聚合物A之構成單體成分所例示之單體相同者。其中，較佳為含有含羥基單體。聚合物P之羥基或羧基成為與下述交聯劑之反應點。藉由對聚合物P導入交聯結構，凝聚力提高，黏著劑層(2)之接著性提高，並且黏著劑之流動性降低，因此有局部去除步驟中於被黏著體之糊劑殘留減少之傾向。The acrylic polymer preferably contains a monomer component having a functional group capable of being crosslinked as a copolymer component. Examples of the monomer having a functional group capable of being crosslinked include a hydroxyl group-containing monomer or a carboxyl group-containing monomer. Examples of the hydroxyl group-containing monomer and the carboxyl group-containing monomer include the same monomers as those exemplified as the constituent monomer components of the polymer A contained in the adhesive layer (1). Among them, it is preferable to contain a hydroxyl-containing monomer. The hydroxyl group or carboxyl group of the polymer P becomes a reaction point with the crosslinking agent described below. By introducing a cross-linked structure to the polymer P, the cohesive force is improved, the adhesiveness of the adhesive layer (2) is improved, and the fluidity of the adhesive is reduced, so there is a tendency for the paste residue in the adherend to be reduced in the partial removal step .

丙烯酸系聚合物中，含羥基單體與含羧基單體之合計量相對於構成單體成分總量較佳為1～30重量%，更佳為3～25重量%，進而較佳為5～20重量%。尤佳為含有羥基之(甲基)丙烯酸酯之含量為上述範圍。In the acrylic polymer, the total amount of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and even more preferably 5 to 30% by weight relative to the total amount of constituent monomer components. 20% by weight. It is particularly preferable that the content of the hydroxyl-containing (meth)acrylate is within the above range.

丙烯酸系聚合物較佳為含有含氮單體作為構成單體成分。作為含氮單體之例，可列舉與作為黏著劑層(1)中所含之聚合物A之構成單體成分所例示之單體相同者。含氮單體之含量相對於構成單體成分總量較佳為1～30重量%，更佳為3～25重量%，進而較佳為5～20重量%。丙烯酸系聚合物較佳為於上述範圍內含有N-乙烯基吡咯啶酮作為含氮單體。The acrylic polymer preferably contains a nitrogen-containing monomer as a constituent monomer component. As an example of the nitrogen-containing monomer, the same monomer as exemplified as the constituent monomer component of the polymer A contained in the adhesive layer (1) can be cited. The content of the nitrogen-containing monomer is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and still more preferably 5 to 20% by weight with respect to the total amount of constituent monomer components. The acrylic polymer preferably contains N-vinylpyrrolidone as a nitrogen-containing monomer within the above range.

於丙烯酸系聚合物含有含羥基單體與含氮單體兩者作為單體成分之情形時，有提高黏著劑之凝聚力及透明性之傾向。丙烯酸系聚合物中，含羥基單體與含氮單體之合計量相對於構成單體成分總量較佳為5～50重量%，更佳為10～40重量%，進而較佳為15～35重量%。When the acrylic polymer contains both a hydroxyl-containing monomer and a nitrogen-containing monomer as monomer components, there is a tendency to improve the cohesive force and transparency of the adhesive. In the acrylic polymer, the total amount of the hydroxyl-containing monomer and the nitrogen-containing monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 15 to 50% by weight relative to the total amount of constituent monomer components. 35 wt%.

丙烯酸系聚合物亦可含有上述以外之單體成分，例如含氰基單體、乙烯酯單體、芳香族乙烯基單體、含環氧基單體、乙烯醚單體、含磺基單體、含磷酸基單體、含酸酐基單體等。Acrylic polymers may also contain monomer components other than the above, such as cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, epoxy group-containing monomers, vinyl ether monomers, and sulfo group-containing monomers , Phosphoric acid group-containing monomers, acid anhydride group-containing monomers, etc.

丙烯酸系聚合物中，均聚物之Tg為40℃以上之單體之含量相對於該丙烯酸系聚合物之構成單體成分總量較佳為5～50重量%，更佳為10～40重量%。就抑制局部去除步驟中之糊劑殘留之觀點而言，聚合物P之構成單體成分較佳為含有均聚物之Tg為80℃以上之單體成分，更佳為含有均聚物之Tg為100℃以上之單體成分。丙烯酸系聚合物中，均聚物之Tg為100℃以上之單體之含量相對於構成單體成分總量較佳為0.1重量%以上，更佳為0.5重量%以上，進而較佳為1重量%以上，尤佳為3重量%以上。尤佳為MMA之含量為上述範圍。再者，用作聚合物P之丙烯酸系聚合物之Tg之較佳範圍可與上述聚合物A之較佳之Tg相同。In the acrylic polymer, the content of the monomer with a Tg of 40°C or higher in the homopolymer is preferably 5-50% by weight, more preferably 10-40% by weight, relative to the total amount of monomer components of the acrylic polymer %. From the viewpoint of suppressing the paste residue in the partial removal step, the constituent monomer component of the polymer P preferably contains a homopolymer with a Tg of 80°C or higher, and more preferably contains a homopolymer with a Tg It is a monomer component above 100°C. In the acrylic polymer, the content of the monomer having a Tg of 100°C or higher in the homopolymer is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and still more preferably 1% by weight relative to the total amount of constituent monomer components % Or more, particularly preferably 3% by weight or more. It is particularly preferable that the content of MMA is in the above range. Furthermore, the preferable range of the Tg of the acrylic polymer used as the polymer P may be the same as the preferable Tg of the above-mentioned polymer A.

丙烯酸系聚合物可與黏著劑層(1)中所含之聚合物A同樣地藉由公知之各種聚合方法而獲得。例如可良好地採用溶液聚合法。The acrylic polymer can be obtained by various known polymerization methods in the same manner as the polymer A contained in the adhesive layer (1). For example, the solution polymerization method can be suitably used.

光硬化前之黏著劑層之接著力容易受聚合物P之構成成分及分子量影響。就同時實現適度之接著性與局部去除步驟中之糊劑殘留之抑制之觀點而言，丙烯酸系聚合物之重量平均分子量較佳為10萬～500萬，更佳為30萬～300萬，進而較佳為50萬～200萬。再者，於對聚合物P導入交聯結構之情形時，聚合物P之分子量係指導入交聯結構前之分子量。The adhesive force of the adhesive layer before photocuring is easily affected by the composition and molecular weight of the polymer P. From the viewpoint of achieving both moderate adhesion and suppression of paste residue in the partial removal step, the weight average molecular weight of the acrylic polymer is preferably 100,000 to 5 million, more preferably 300,000 to 3 million, and further It is preferably 500,000 to 2 million. Furthermore, when a cross-linked structure is introduced into the polymer P, the molecular weight of the polymer P is the molecular weight before the cross-linked structure is introduced.

(交聯劑) 就使黏著劑具有適度之凝聚力之觀點而言，較佳為對聚合物P導入交聯結構。例如藉由於使聚合物P聚合後之溶液中添加交聯劑，且視需要進行加熱，而導入交聯結構。作為交聯劑，可列舉：異氰酸酯系交聯劑、環氧系交聯劑、

Figure 108128671-A0304-12-02
唑啉系交聯劑、氮丙啶系交聯劑、碳二醯亞胺系交聯劑、金屬螯合物系交聯劑等。該等交聯劑與導入至聚合物P之羥基等官能基進行反應而形成交聯結構。作為異氰酸酯系交聯劑，可使用與黏著劑層(1)相同者。(Crosslinking agent) It is preferable to introduce a crosslinking structure to the polymer P from the viewpoint of giving the adhesive a moderate cohesive force. For example, the crosslinking structure is introduced by adding a crosslinking agent to the solution after polymerizing the polymer P, and heating as necessary. Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents,
Figure 108128671-A0304-12-02
Oxazoline-based cross-linking agents, aziridine-based cross-linking agents, carbodiimide-based cross-linking agents, metal chelate-based cross-linking agents, etc. These crosslinking agents react with functional groups such as hydroxyl groups introduced into the polymer P to form a crosslinked structure. As the isocyanate-based crosslinking agent, the same as the adhesive layer (1) can be used.

交聯劑之使用量只要根據聚合物P之組成或分子量等而適當調整即可。交聯劑之使用量相對於100重量份聚合物P，例如可為0.1～10重量份左右，較佳為0.3～7重量份，更佳為0.5～5重量份，進而較佳為1～4重量份。為了促進交聯結構之形成，亦可與黏著劑層(1)同樣地使用交聯觸媒。The amount of the crosslinking agent used may be appropriately adjusted according to the composition or molecular weight of the polymer P. The amount of crosslinking agent used relative to 100 parts by weight of polymer P may be, for example, about 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, and still more preferably 1 to 4 parts by weight. Parts by weight. In order to promote the formation of a cross-linked structure, a cross-linking catalyst can also be used in the same manner as the adhesive layer (1).

(光硬化劑) 構成黏著劑層(2)之黏著劑組合物構成為，藉由除含有聚合物P以外亦含有光硬化劑而顯示出光硬化性。黏著劑層(2)顯示出如下性質：藉由在與被黏著體貼合後進行活性光線之照射作為使黏著力上升之刺激，而進行光硬化，黏著力提高。(Light Hardener) The adhesive composition constituting the adhesive layer (2) is configured to exhibit photocurability by containing a photocuring agent in addition to the polymer P. The adhesive layer (2) exhibits the following properties: by irradiating with active light as a stimulus to increase the adhesive force after being attached to the adherend, the adhesive is photocured to improve the adhesive force.

作為光硬化劑，可使用光硬化性單體、或光硬化性低聚物。作為光硬化劑，較佳為於1分子中具有2個以上之乙烯性不飽和鍵之化合物。又，光硬化劑較佳為顯示出與聚合物P之相溶性之化合物。就顯示出與聚合物P之適度之相溶性之方面而言，光硬化劑較佳為於常溫下為液體者。藉由光硬化劑與聚合物P相溶，於組合物中均勻地分散，而能夠確保與被黏著體之接觸面積，且可形成透明性較高之黏著劑層(2)。As the photocuring agent, a photocuring monomer or a photocuring oligomer can be used. As the light curing agent, a compound having two or more ethylenically unsaturated bonds in one molecule is preferred. In addition, the light hardener is preferably a compound showing compatibility with the polymer P. In terms of showing moderate compatibility with the polymer P, the light hardener is preferably one that is liquid at room temperature. By dissolving the light hardener and the polymer P and uniformly dispersing in the composition, the contact area with the adherend can be ensured, and the adhesive layer (2) with higher transparency can be formed.

聚合物P與光硬化劑之相溶性主要受到化合物之結構之影響。化合物之結構與相溶性例如可藉由Hansen溶解度參數進行評價，有聚合物P與光硬化劑之溶解度參數之差越小則相溶性變得越高之傾向。The compatibility of the polymer P and the light hardener is mainly affected by the structure of the compound. The structure and compatibility of the compound can be evaluated by the Hansen solubility parameter, for example. The smaller the difference between the solubility parameter of the polymer P and the light hardener, the higher the compatibility.

就與丙烯酸系聚合物之相溶性較高之方面而言，較佳為使用多官能(甲基)丙烯酸酯作為光硬化劑。作為多官能(甲基)丙烯酸酯，可列舉：聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚四亞甲基二醇二(甲基)丙烯酸酯、雙酚A環氧乙烷改性二(甲基)丙烯酸酯、雙酚A環氧丙烷改性二(甲基)丙烯酸酯、烷二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、乙氧基化異三聚氰酸三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、環氧(甲基)丙烯酸酯、丁二烯(甲基)丙烯酸酯、異戊二烯(甲基)丙烯酸酯等。In terms of high compatibility with the acrylic polymer, it is preferable to use a polyfunctional (meth)acrylate as a light hardening agent. Examples of polyfunctional (meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, Bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol A propylene oxide modified di(meth)acrylate, alkanediol di(meth)acrylate, tricyclodecane dimethanol Di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri( Meth) acrylate, bis(trimethylolpropane) tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate )Acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, (meth)acrylate urethane, epoxy(meth)acrylate Yl)acrylate, butadiene (meth)acrylate, isoprene (meth)acrylate, etc.

聚合物P與光硬化劑之相溶性亦受化合物之分子量影響。有光硬化性化合物之分子量越小則與聚合物P之相溶性變得越高之傾向。就與聚合物P之相溶性之觀點而言，光硬化劑之分子量較佳為1500以下，更佳為1000以下。The compatibility of the polymer P and the light hardener is also affected by the molecular weight of the compound. The lower the molecular weight of the photocurable compound, the higher the compatibility with the polymer P tends to be. From the viewpoint of compatibility with the polymer P, the molecular weight of the light hardener is preferably 1500 or less, more preferably 1000 or less.

光硬化劑之種類或含量主要對光硬化後之黏著力產生影響。有官能基當量越小(即，每單位分子量之官能基數越大)，光硬化劑之含量越大，則光硬化後之黏著力變得越大之傾向。The type or content of light hardener mainly affects the adhesion after light hardening. There is a tendency that the smaller the functional group equivalent (that is, the greater the number of functional groups per unit molecular weight) and the greater the content of the light hardening agent, the greater the adhesive force after light hardening.

就提高光硬化後之黏著力之觀點而言，光硬化劑之官能基當量(g/eq)較佳為500以下，更佳為450以下。另一方面，若光交聯密度過度地上升，則有黏著劑之黏性降低而導致黏著力降低之情形。因此，光硬化劑之官能基當量較佳為100以上，更佳為130以上，進而較佳為150以上，尤佳為180以上。From the viewpoint of improving the adhesive force after photocuring, the functional group equivalent (g/eq) of the photocuring agent is preferably 500 or less, and more preferably 450 or less. On the other hand, if the photo-crosslinking density increases excessively, the viscosity of the adhesive may decrease, resulting in a decrease in adhesive strength. Therefore, the functional group equivalent of the light hardener is preferably 100 or more, more preferably 130 or more, still more preferably 150 or more, and particularly preferably 180 or more.

於丙烯酸系聚合物與多官能丙烯酸酯光硬化劑之組合中，於光硬化劑之官能基當量較小之情形時，聚合物P與光硬化劑之相互作用較強，有光硬化前之黏著力變高之傾向。於此處所揭示之技術中，就將光硬化前之黏著力抑制為適當之範圍而提高局部去除步驟中之第二區域之去除性之觀點而言，亦較佳為光硬化劑之官能基當量為上述範圍內。In the combination of acrylic polymer and multifunctional acrylate light hardener, when the functional group equivalent of the light hardener is small, the interaction between the polymer P and the light hardener is stronger, and there is adhesion before light hardening The tendency to become higher. In the technology disclosed here, from the viewpoint of suppressing the adhesive force before photocuring to an appropriate range and improving the removability of the second region in the partial removal step, the functional group equivalent of the photocuring agent is also preferred Within the above range.

黏著劑組合物中之光硬化劑之含量相對於100重量份聚合物P，較佳為1～50重量份，更佳為5～40重量份，進而較佳為10～35重量份。藉由使光硬化性化合物以未硬化(未反應)之單體或低聚物之形式含有於黏著劑組合物中，可獲得光硬化性之黏著劑層。為了使光硬化劑於未硬化之狀態下含有於組合物中，較佳為於使聚合物P聚合後之聚合物溶液中添加光硬化劑。The content of the light hardener in the adhesive composition is preferably 1-50 parts by weight, more preferably 5-40 parts by weight, and still more preferably 10-35 parts by weight relative to 100 parts by weight of polymer P. By containing the photocurable compound in the form of an uncured (unreacted) monomer or oligomer in the adhesive composition, a photocurable adhesive layer can be obtained. In order to include the light hardening agent in the composition in an uncured state, it is preferable to add the light hardening agent to the polymer solution after polymerizing the polymer P.

若黏著劑組合物中之光硬化劑之含量變大，則光硬化劑容易滲出至黏著劑層之表面。若光硬化劑大量地滲出，則容易於去除第二區域後之被黏著體殘留光硬化劑。另一方面，藉由使少量之光硬化劑滲出至表面，能夠抑制黏著劑層對被黏著體之黏著力，良好地同時實現光硬化前之低黏著性與光硬化後之強黏著性。If the content of the light hardener in the adhesive composition becomes larger, the light hardener will easily ooze out to the surface of the adhesive layer. If the light hardener oozes out in a large amount, the light hardener is likely to remain on the adherend after removing the second area. On the other hand, by allowing a small amount of light hardening agent to ooze out to the surface, the adhesive force of the adhesive layer to the adherend can be suppressed, and the low adhesiveness before light curing and the strong adhesiveness after light curing can be achieved simultaneously.

(光起始劑) 黏著劑層(2)較佳為含有光起始劑。光起始劑藉由活性光線之照射產生活性種，促進光硬化劑之硬化反應。作為光起始劑，可根據光硬化劑之種類等而使用光陽離子起始劑(光酸產生劑)、光自由基起始劑、光陽離子起始劑(光鹼產生劑)等。於使用多官能丙烯酸酯作為光硬化劑之情形時，較佳為使用光自由基起始劑。作為光自由基起始劑，可列舉：羥基酮類、苯偶醯二甲基縮酮類、胺基酮類、醯基氧化膦類、二苯甲酮類、含三氯甲基之三

Figure 108128671-A0304-12-01
衍生物等。光自由基產生劑可單獨使用，亦可混合兩種以上使用。黏著劑層中之光起始劑之含量相對於黏著劑層之總量100重量份較佳為0.001～10重量份，更佳為0.01～5重量份。(Photoinitiator) The adhesive layer (2) preferably contains a photoinitiator. The photoinitiator generates active species through the irradiation of active light to promote the hardening reaction of the photohardener. As the photoinitiator, a photocation initiator (photoacid generator), a photoradical initiator, a photocation initiator (photobase generator), etc. can be used according to the kind of the photohardener or the like. In the case of using a multifunctional acrylate as a light hardener, it is preferable to use a light radical initiator. Examples of photoradical initiators include: hydroxy ketones, benzyl dimethyl ketals, amino ketones, phosphine oxides, benzophenones, trichloromethyl-containing tertiary
Figure 108128671-A0304-12-01
Derivatives etc. The light radical generator can be used alone or in combination of two or more. The content of the photoinitiator in the adhesive layer is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight relative to 100 parts by weight of the total amount of the adhesive layer.

(其他添加劑) 除上述例示之各成分以外，黏著劑層亦可於不會較大地損及藉由此處所揭示之技術所獲得之效果之範圍內含有矽烷偶合劑、黏著性賦予劑、塑化劑、軟化劑、抗劣化劑、填充劑、著色劑、紫外線吸收劑、抗氧化劑、界面活性劑、抗靜電劑等添加劑。(Other additives) In addition to the components exemplified above, the adhesive layer may also contain a silane coupling agent, an adhesive imparting agent, a plasticizer, and a softening agent within a range that does not greatly impair the effects obtained by the technology disclosed here. , Anti-deterioration agents, fillers, colorants, ultraviolet absorbers, antioxidants, surfactants, antistatic agents and other additives.

(黏著劑層之形成) 黏著劑層(2)例如可藉由將含有聚合物P、光硬化劑及視需要使用之其他成分之黏著劑組合物塗佈於適當之表面後，視需要將溶劑乾燥去除而形成。作為乾燥方法，可適當採用適當之方法。加熱乾燥溫度較佳為40℃～200℃，更佳為50℃～180℃，進而較佳為70℃～170℃。乾燥時間較佳為5秒～20分鐘，更佳為5秒～15分鐘，進而較佳為10秒～10分鐘。(Formation of Adhesive Layer) The adhesive layer (2) can be formed, for example, by coating an adhesive composition containing polymer P, a light hardener, and other components as needed on an appropriate surface, and then drying and removing the solvent as needed. As the drying method, an appropriate method can be appropriately adopted. The heating and drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and still more preferably 70°C to 170°C. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and still more preferably 10 seconds to 10 minutes.

於黏著劑組合物含有交聯劑之情形時，較佳為於溶劑之乾燥之同時、或於溶劑之乾燥後藉由加熱或老化進行交聯。加熱溫度或加熱時間係根據所使用之交聯劑之種類而適當設定，通常於20℃～160℃之範圍內，藉由1分鐘～7天左右之加熱進行交聯。用於將溶劑乾燥去除之加熱亦可兼作用於交聯之加熱。於藉由交聯劑對聚合物導入交聯結構後，光硬化劑亦維持未反應之狀態。因此，形成包含導入了交聯結構之聚合物P與未反應之光硬化劑之光硬化性黏著劑層(2)。When the adhesive composition contains a cross-linking agent, it is preferable to perform cross-linking by heating or aging simultaneously with the drying of the solvent or after the drying of the solvent. The heating temperature or heating time is appropriately set according to the type of crosslinking agent used, and is usually within the range of 20°C to 160°C, and crosslinking is performed by heating for about 1 minute to 7 days. The heating used to dry and remove the solvent can also act as the heating for crosslinking. After the cross-linking structure is introduced into the polymer by the cross-linking agent, the light hardener also maintains an unreacted state. Therefore, a light-curing adhesive layer (2) containing the polymer P with the cross-linked structure introduced and the unreacted light-curing agent is formed.

(摩擦力) 關於光硬化前之黏著劑層(2)，就容易抑制黏著力之觀點而言，較佳為藉由摩擦力顯微鏡(FFM)之輕敲模式測得之頻率5 Hz下之摩擦力為頻率0.1 Hz下之摩擦力之2～5倍。又，於黏著劑層(2)之頻率0.1 Hz與5 Hz之摩擦力之比處於該範圍之情形時，有容易使光硬化後之黏著力較光硬化前大幅地上升之傾向。(Friction) Regarding the adhesive layer (2) before photocuring, from the viewpoint of easily suppressing the adhesive force, it is preferable that the friction force measured by the tapping mode of the friction force microscope (FFM) at a frequency of 5 Hz is a frequency of 0.1 2 to 5 times the friction under Hz. In addition, when the ratio of the frictional force between the frequency of 0.1 Hz and the frequency of 5 Hz of the adhesive layer (2) is in this range, the adhesive force after photocuring tends to increase significantly compared to before photocuring.

於FFM中，將於掃描式探針顯微鏡(SPM)之探針與試樣表面之間作用之力轉換為懸臂之板彈簧之位移(扭轉量)，電性地檢測出該位移。位移量與差分電壓成比例，摩擦力與懸臂之彈簧常數及位移量成比例。因此，摩擦力與FFM差分電壓成比例。頻率5 Hz下之摩擦力與頻率0.1 Hz下之摩擦力之比與兩者之FFM差分信號之比相等。In FFM, the force acting between the probe of the scanning probe microscope (SPM) and the sample surface is converted into the displacement (torsion) of the cantilever leaf spring, and the displacement is detected electrically. The displacement is proportional to the differential voltage, and the friction force is proportional to the spring constant and displacement of the cantilever. Therefore, the frictional force is proportional to the FFM differential voltage. The ratio of the frictional force at a frequency of 5 Hz to the frictional force at a frequency of 0.1 Hz is equal to the ratio of the FFM differential signal between the two.

由奈米摩擦學所獲得之摩擦力有反映出黏著劑層之表面與被黏著體之接著性之傾向，摩擦力較小意味著黏著劑之表面接近於液狀，黏性較小。於黏著劑層之表面具有黏性之情形時，摩擦力變大，並且藉由FFM所測定之摩擦力呈現出頻率依存性。於特定之頻率下測定之摩擦力容易反映出黏著劑組合物之構成成分各者之物性，相對於此，頻率依存有更確實地反映出表面之特性之傾向。摩擦力之頻率依存越小，表示黏性越小，液狀之特性越強，摩擦力之頻率依存越大，則有黏性越大，對被黏著體之接著性變得越高之傾向。例如，於黏著劑層之基礎聚合物與光硬化劑並非完全相溶系之情形時，液狀之光硬化劑滲出至表面，而於與被黏著體之接著界面形成接著阻礙層(WBL，Weak Boundary Layer)，液狀之特性變強，因此有摩擦力及摩擦力之頻率依存變小之傾向。The friction force obtained from nanotribology has a tendency to reflect the adhesion between the surface of the adhesive layer and the adherend. Smaller friction means that the surface of the adhesive is close to liquid and less viscous. When the surface of the adhesive layer is sticky, the frictional force becomes larger, and the frictional force measured by FFM shows frequency dependence. The friction force measured at a specific frequency easily reflects the physical properties of the constituent components of the adhesive composition. In contrast, the frequency dependence tends to reflect the characteristics of the surface more reliably. The smaller the frequency dependence of friction, the smaller the viscosity and the stronger the liquid characteristics. The greater the frequency dependence of friction, the greater the viscosity and the higher the adherence to the adherend. For example, when the base polymer of the adhesive layer and the light hardener are not completely compatible, the liquid light hardener oozes out to the surface, and an adhesion barrier layer (WBL, Weak Boundary) is formed at the adhesion interface with the adherend. Layer), the liquid characteristics become stronger, so there is a tendency for friction and the frequency dependence of friction to become smaller.

藉由控制黏著劑層(2)中之聚合物P與光硬化劑之相溶性，有少量之光硬化劑滲出至黏著劑層表面而形成WBL之情形。若適度地形成WBL，則表面(接著界面)之特性發生變化，摩擦力及摩擦力之頻率依存變小。藉此，變得容易抑制光硬化前之黏著力，於該光硬化前進行局部去除步驟之情形時之第二區域之剝離變得容易。By controlling the compatibility of the polymer P and the light hardener in the adhesive layer (2), a small amount of the light hardener oozes out to the surface of the adhesive layer to form WBL. If WBL is appropriately formed, the characteristics of the surface (adhered to the interface) will change, and the friction force and the frequency dependence of the friction force will become smaller. Thereby, it becomes easy to suppress the adhesive force before photocuring, and it becomes easy to peel off the second area when the partial removal step is performed before the photocuring.

於光硬化前之黏著劑層之頻率5 Hz下之摩擦力為頻率0.1 Hz下之摩擦力之5倍以下之情形時，有光硬化前之黏著劑層與被黏著體之剝離變得容易之傾向。就避免光硬化劑之滲出之觀點而言，黏著劑層之頻率5 Hz下之摩擦力較佳為頻率0.1 Hz下之摩擦力之2倍以上，更佳為3倍以上，進而較佳為3.5倍以上。When the friction force of the adhesive layer before photocuring at a frequency of 5 Hz is less than 5 times the friction force at a frequency of 0.1 Hz, the peeling of the adhesive layer and the adherend before photocuring becomes easier tendency. From the viewpoint of avoiding the bleeding of the light hardener, the friction force of the adhesive layer at a frequency of 5 Hz is preferably at least twice the friction at a frequency of 0.1 Hz, more preferably at least 3 times, and even more preferably 3.5 Times more.

就同時實現對被黏著體之適度之接著性與剝離性之觀點而言，使用彈簧常數40 N/m之懸臂測得之光硬化前之黏著劑層於頻率5 Hz下之FFM差分信號較佳為0.01～1 V，更佳為0.05～0.9 V，進而較佳為0.1～0.8 V，尤佳為0.2～0.7 V。From the viewpoint of achieving proper adhesion and peelability to the adherend at the same time, it is better to use the FFM differential signal of the adhesive layer before photohardening measured by a cantilever with a spring constant of 40 N/m at a frequency of 5 Hz It is 0.01 to 1 V, more preferably 0.05 to 0.9 V, still more preferably 0.1 to 0.8 V, and particularly preferably 0.2 to 0.7 V.

就提高光硬化後之黏著力之觀點而言，較佳為光硬化後之黏著劑層藉由FFM所測得之頻率5 Hz下之摩擦力為頻率0.1 Hz下之摩擦力之5倍以上，更佳為5.5倍以上。使用彈簧常數40 N/m之懸臂測得之光硬化後之黏著劑層於頻率5 Hz下之FFM差分信號較佳為0.1 V以上，更佳為0.2 V以上，進而較佳為0.3 V以上。就提高黏著力之觀點而言，光硬化後之黏著劑層之摩擦力越大越佳。因此，摩擦力之上限並無特別限制，使用彈簧常數40 N/m之懸臂測得之5 Hz下之FFM差分信號一般為10 V以下，若考慮黏著劑之特性之平衡，則較佳為5 V以下。From the viewpoint of improving the adhesive force after photocuring, it is preferable that the friction force of the adhesive layer after photocuring measured by FFM at a frequency of 5 Hz is more than 5 times the friction force at a frequency of 0.1 Hz. More preferably, it is 5.5 times or more. The FFM differential signal of the adhesive layer after photohardening measured using a cantilever with a spring constant of 40 N/m at a frequency of 5 Hz is preferably 0.1 V or more, more preferably 0.2 V or more, and more preferably 0.3 V or more. From the viewpoint of improving the adhesive force, the greater the friction force of the adhesive layer after light curing, the better. Therefore, the upper limit of the friction force is not particularly limited. The FFM differential signal at 5 Hz measured with a cantilever with a spring constant of 40 N/m is generally below 10 V. If the balance of the adhesive characteristics is considered, it is preferably 5 Below V.

光硬化後之黏著劑層於頻率5 Hz下之摩擦力較佳為光硬化前之黏著劑層於頻率5 Hz下之摩擦力之1.5倍以上，更佳為2倍以上，進而較佳為2.5倍以上，尤佳為3倍以上。有光硬化前後之摩擦力之比越大，則利用光硬化所產生之接著力之增加率變得越高之傾向。光硬化後之摩擦力一般為光硬化前之摩擦力之20倍以下，較佳為10倍以下。The friction force of the adhesive layer after photocuring at a frequency of 5 Hz is preferably at least 1.5 times the friction force of the adhesive layer before photocuring at a frequency of 5 Hz, more preferably at least 2 times, and more preferably 2.5 Times or more, more preferably 3 times or more. There is a tendency that the greater the ratio of friction before and after photocuring, the higher the increase rate of adhesive force produced by photocuring. The friction force after photocuring is generally 20 times or less than the friction force before photocuring, preferably 10 times or less.

再者，光硬化前及光硬化後之黏著劑層於頻率0.1 Hz及5 Hz下之摩擦力係藉由於掃描式探針顯微鏡(Hitachi High-Tech Science製造之「AFM5300E」)之FFM模式下，藉由下述條件，以單向之掃描寬度5 μm(往返掃描10 μm)進行摩擦測定，讀取自測定範圍之左側起3 μm之位置上之差分電壓而測得。 (測定條件) 懸臂：BudgetSensors製造之「Tap300E-G」(相當於彈簧常數40 N/m者) ADD值：8.44 V、DIF值：0.4 V、FFM值：0 V 環境：真空、室溫 掃描速度：0.1 Hz、1 Hz及5 HzFurthermore, the friction force of the adhesive layer before and after photocuring at frequencies of 0.1 Hz and 5 Hz is due to the scanning probe microscope ("AFM5300E" manufactured by Hitachi High-Tech Science) in the FFM mode. Under the following conditions, the friction measurement was performed with a one-way scan width of 5 μm (a reciprocating scan 10 μm), and the measurement was made by reading the differential voltage at a position 3 μm from the left side of the measurement range. (Measurement conditions) Cantilever: "Tap300E-G" made by BudgetSensors (equivalent to a spring constant of 40 N/m) ADD value: 8.44 V, DIF value: 0.4 V, FFM value: 0 V Environment: vacuum, room temperature Scanning speed: 0.1 Hz, 1 Hz and 5 Hz

作為可用於黏著劑層(2)之光硬化之活性光線之例，可列舉紫外線(UV)、可見光、紅外線、X射線、α射線、β射線、及γ射線等。就容易抑制保管狀態下之黏著劑層之硬化且容易硬化之方面而言，作為活性光線，較佳為UV。活性光線之照射強度或照射時間只要根據黏著劑層之組成或厚度等適當設定即可。Examples of active rays that can be used for photohardening of the adhesive layer (2) include ultraviolet (UV), visible light, infrared, X-ray, α-ray, β-ray, and γ-ray. In terms of easily suppressing the hardening of the adhesive layer in the storage state and easy hardening, the active light is preferably UV. The irradiation intensity or irradiation time of the active light can be appropriately set according to the composition or thickness of the adhesive layer.

黏著劑層(2)為光硬化性，可任意地設定藉由硬化使黏著力上升之時刻。因此，於將黏著片材貼設於被黏著體後，能夠在使黏著劑光硬化之前的期間之任意時刻實施局部去除步驟，能夠靈活地應對裝置之製造步驟之準備時間。The adhesive layer (2) is light-curable, and the time at which the adhesive force increases by curing can be arbitrarily set. Therefore, after attaching the adhesive sheet to the adherend, the partial removal step can be performed at any time during the period before the adhesive is photocured, and the preparation time for the manufacturing step of the device can be flexibly dealt with.

＜黏著片材之構造＞ 此處所揭示之製造方法所使用之黏著片材之厚度並無特別限定，例如可為3 μm～11 mm左右。就黏著片材之操作性等觀點而言，黏著片材之厚度通常適宜為5 μm以上，可為10 μm以上，亦可為30 μm以上。就局部去除步驟中之第二區域之剝離作業性等觀點而言，於若干種態樣中，可良好地使用厚度為50 μm以上、70 μm以上或90 μm以上之黏著片材。又，就切割步驟中之切斷加工性或局部去除步驟中之第二區域之剝離作業性等觀點而言，黏著片材之厚度例如可為1000 μm以下，可為600 μm以下，可為350 μm以下，可為200 μm以下，亦可為150 μm以下。＜The structure of the adhesive sheet＞ The thickness of the adhesive sheet used in the manufacturing method disclosed here is not particularly limited, and may be, for example, about 3 μm to 11 mm. From the viewpoint of handling properties of the adhesive sheet, the thickness of the adhesive sheet is usually preferably 5 μm or more, may be 10 μm or more, or may be 30 μm or more. From the viewpoint of the peeling workability of the second area in the partial removal step, in several aspects, an adhesive sheet with a thickness of 50 μm or more, 70 μm or more, or 90 μm or more can be used well. In addition, from the viewpoints of cutting processability in the cutting step or peeling workability of the second region in the partial removal step, the thickness of the adhesive sheet may be, for example, 1000 μm or less, 600 μm or less, or 350 μm or less, 200 μm or less, or 150 μm or less.

於包含基材層與黏著劑層之黏著片材中，黏著劑層之厚度並無特別限定，例如可設為1 μm～1000 μm左右之範圍。於若干種態樣中，黏著劑層之厚度例如可為3 μm以上，可為5 μm以上，可為8 μm以上，可為10 μm以上，可為13 μm以上，亦可為20 μm以上或超過20 μm。藉由增大黏著劑層之厚度，有獲得黏著片更牢固地接合於被黏著體之積層體之傾向。另一方面，若黏著劑層之厚度過大，則可能有因第一區域之黏著劑與第二區域之黏著劑之黏連等而導致局部去除步驟中之作業性(例如第一區域與第二區域之分離性)降低之傾向。就該觀點而言，黏著劑層之厚度例如可為300 μm以下，可為200 μm以下，可為150 μm以下，可為100 μm以下，可為70 μm以下，可為50 μm以下，可為40 μm以下，亦可為30 μm以下。In the adhesive sheet including the base layer and the adhesive layer, the thickness of the adhesive layer is not particularly limited, and for example, it can be set to a range of about 1 μm to 1000 μm. In some aspects, the thickness of the adhesive layer can be, for example, 3 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 13 μm or more, or 20 μm or more. More than 20 μm. By increasing the thickness of the adhesive layer, there is a tendency to obtain a laminate in which the adhesive sheet is more firmly bonded to the adherend. On the other hand, if the thickness of the adhesive layer is too large, the adhesion between the adhesive in the first area and the adhesive in the second area may cause the workability in the partial removal step (such as the first area and the second area). The separation of regions) tends to decrease. From this point of view, the thickness of the adhesive layer can be, for example, 300 μm or less, 200 μm or less, 150 μm or less, 100 μm or less, 70 μm or less, 50 μm or less, or 40 μm or less, but also 30 μm or less.

於包含基材層與黏著劑層之黏著片材中，基材層之厚度並無特別限定，例如可為2 μm～10 mm左右。就黏著片材之操作性或防止局部去除步驟中之第二區域之破裂之觀點而言，於若干種態樣中，基材層之厚度例如可為5 μm以上，可為10 μm以上，可為25 μm以上，可為35 μm以上，可為50 μm以上，亦可為60 μm以上。又，就切割步驟中之切斷加工性等觀點而言，於若干種態樣中，基材層之厚度例如可為1000 μm以下，可為500 μm以下，可為300 μm以下，可為200 μm以下，可為150 μm以下，可為100 μm以下，亦可為90 μm以下。In the adhesive sheet including the base layer and the adhesive layer, the thickness of the base layer is not particularly limited, and may be, for example, about 2 μm to 10 mm. From the viewpoint of the operability of the adhesive sheet or the prevention of cracks in the second region in the partial removal step, in some aspects, the thickness of the substrate layer may be, for example, 5 μm or more, 10 μm or more, or It is 25 μm or more, may be 35 μm or more, may be 50 μm or more, or may be 60 μm or more. In addition, from the viewpoint of cutting processability in the cutting step, in some aspects, the thickness of the substrate layer may be 1000 μm or less, 500 μm or less, 300 μm or less, or 200 μm or less. μm or less, may be 150 μm or less, may be 100 μm or less, or may be 90 μm or less.

此處所揭示之製造方法所使用之黏著片材可以基材層之厚度Ts大於黏著劑層之厚度Ta之態樣良好地實施。即，較佳為Ts/Ta大於1。Ts/Ta例如可為1.1以上，可為1.2以上，可為1.5以上，可為2以上，亦可為2.5以上，但並無特別限定。又，Ts/Ta例如可為50以下，可為20以下，可為10以下，亦可為7以下。藉由使用滿足上述任一上限值且/或滿足上述任一下限值之構成之黏著片材，有平衡性良好地同時實現局部去除步驟中之良好之剝離作業性與最終獲得之積層體之黏著片對被黏著體之牢固之接著性之傾向。The adhesive sheet used in the manufacturing method disclosed herein can be implemented well in a state where the thickness Ts of the substrate layer is greater than the thickness Ta of the adhesive layer. That is, it is preferable that Ts/Ta is greater than 1. Ts/Ta may be 1.1 or more, 1.2 or more, 1.5 or more, 2 or more, or 2.5 or more, for example, but it is not particularly limited. In addition, Ts/Ta may be 50 or less, 20 or less, 10 or less, or 7 or less, for example. By using an adhesive sheet that satisfies any of the above upper limits and/or satisfies any of the above lower limits, it is possible to achieve good peeling workability in the partial removal step and the final laminate body with a good balance. The tendency of the adhesive sheet to adhere firmly to the adherend.

於若干種態樣中，用於貼附步驟之黏著片材例如可為面積為2500 cm2 以上且短邊之長度為50 cm以上。於使用如上所述大尺寸之黏著片材之態樣中，採用此處所揭示之製造方法尤其有意義。藉由使用該黏著片材，有良好地發揮例如提高位置精度、提高形狀精度、提高生產性等中之一種或兩種以上之效果的傾向。又，根據此處所揭示之製造方法，於黏著片材對被黏著體之黏著力超過2 N/25 mm之前進行將該黏著片材之第二區域剝離去除之局部去除步驟，因此即便為如上所述大尺寸之黏著片材，亦容易進行第二區域之剝離去除。根據上述黏著片材之面積為3600 cm2 以上、更佳為4900 cm2 以上之態樣、或上述短邊之長度為60 cm以上、更佳為70 cm以上之態樣，可發揮更高之效果。In some aspects, the adhesive sheet used in the attaching step may have an area of 2500 cm 2 or more and the length of the short side of 50 cm or more, for example. In the case of using the above-mentioned large size adhesive sheet, it is particularly meaningful to adopt the manufacturing method disclosed here. By using this adhesive sheet, there is a tendency that one or two or more of the effects of improving position accuracy, improving shape accuracy, and improving productivity tend to be exerted well. Furthermore, according to the manufacturing method disclosed here, the local removal step of peeling and removing the second area of the adhesive sheet is performed before the adhesive force of the adhesive sheet to the adherend exceeds 2 N/25 mm, so even if it is as above The large size of the adhesive sheet is also easy to peel off the second area. According to the aspect that the area of the adhesive sheet is 3600 cm 2 or more, more preferably 4900 cm 2 or more, or the aspect that the length of the short side is 60 cm or more, and more preferably 70 cm or more, it can achieve higher performance effect.

＜用途＞ 根據此處所揭示之方法，可高效率地製造於被黏著體上精度良好地形成有黏著片之圖案且上述圖案之耐久性優異之積層體。利用該優勢，此處所揭示之方法可良好地應用於製造將車輛之外裝材或內裝材、建築物之外裝材或內裝材等建材、窗玻璃、看板、標識、家電製品、光學製品、電子製品等製品或其構成構件作為被黏著體，且利用黏著片之圖案局部地覆蓋此種被黏著體的積層體之用途。上述積層體可為上述各種製品或其構成構件。上述黏著片藉由作為上述積層體之構成要素包含於各種製品，可有助於對該積層體中所含之被黏著體、或包含上述積層體之製品或其構件賦予裝飾、顯示、保護、補強、衝擊緩和、應力集中之緩和、形狀維持、形狀恢復等功能。此處所揭示之方法例如可良好地應用於具備膜覆蓋層之FPC之製造。<Use> According to the method disclosed here, it is possible to efficiently manufacture a laminate in which the pattern of the adhesive sheet is accurately formed on the adherend and the pattern is excellent in durability. Taking advantage of this advantage, the method disclosed here can be well applied to the manufacture of building materials such as vehicle exterior or interior materials, building exterior or interior materials, window glass, signage, signs, home appliances, optical Products such as products and electronic products or their constituent members are used as adherends, and the laminated body of such adherends is partially covered by the pattern of the adhesive sheet. The above-mentioned laminate may be the above-mentioned various products or their constituent members. The above-mentioned adhesive sheet is included in various products as a constituent element of the above-mentioned laminated body, and can contribute to impart decoration, display, protection, and protection to the adherend contained in the laminated body, or the product containing the above-mentioned laminated body or its members. Reinforcement, impact relaxation, stress concentration relaxation, shape maintenance, shape recovery and other functions. The method disclosed here can be well applied to the manufacture of FPC with a film covering layer, for example.

又，關於用於光學製品之光學構件或用於電子製品之電子構件，高度之積體化、小型輕量化、薄型化不斷發展，可積層線膨脹係數或厚度不同之複數個較薄之光學構件/電子構件。藉由將此種構件作為被黏著體，利用此處所揭示之方法形成上述構件經黏著片局部地覆蓋之積層體，可對上述光學構件/電子構件賦予適度之剛性。藉此，於製造製程及/或製造後之製品中，可抑制因上述線膨脹係數或厚度不同之複數個構件間可能產生之應力所導致之捲曲或彎曲。In addition, with regard to optical components used in optical products or electronic components used in electronic products, high integration, miniaturization, weight reduction, and thinning continue to develop. It is possible to laminate multiple thinner optical components with different linear expansion coefficients or thicknesses. /Electronic components. By using such a member as an adherend and forming a laminate in which the member is partially covered by an adhesive sheet by the method disclosed herein, moderate rigidity can be imparted to the optical member/electronic member. Thereby, in the manufacturing process and/or the product after manufacturing, curling or bending caused by the stress that may be generated between the plurality of members with different linear expansion coefficients or different thicknesses can be suppressed.

又，於光學製品/電子製品之製造製程中，於如上所述對較薄之光學構件/電子構件進行切斷加工等形狀加工處理之情形時，藉由形成該構件(被黏著體)經黏著片局部地覆蓋之積層體，而可利用上述黏著片作為補強構件，緩和伴隨上述積層體之加工之對光學構件/電子構件之局部之應力集中，可減少龜裂、破裂、積層構件之剝離等風險。對光學構件/電子構件貼附補強構件而進行操作亦可有助於該構件之搬送、積層、旋轉等時之局部之應力集中之緩和、或因該構件之自重所導致之彎折或彎曲之抑制等。In addition, in the optical product/electronic product manufacturing process, when the thin optical component/electronic component is subjected to shape processing such as cutting processing as described above, the component (adhered body) is formed by bonding The laminated body is partially covered by the sheet, and the above-mentioned adhesive sheet can be used as a reinforcing member to alleviate the local stress concentration on the optical component/electronic component accompanying the processing of the laminated body, and reduce cracks, cracks, peeling of the laminated member, etc. risk. The operation of attaching the reinforcing member to the optical member/electronic member can also help to ease the local stress concentration during the transportation, stacking, and rotation of the member, or the bending or bending caused by the weight of the member Restrain etc.

進而，包含被黏著體經上述黏著片之圖案局部地覆蓋之積層體的光學製品或電子製品等裝置於在市場上供消費者使用之階段，即便於該裝置掉落之情形、置於重量物之下之情形、飛來物碰撞之情形等施加意外之應力之情形時，亦可藉由使該裝置中所含之上述黏著片發揮作為補強構件之功能，而緩和施加於裝置之應力，提高耐久性。Furthermore, devices such as optical products or electronic products including a laminated body in which the adherend is partially covered by the pattern of the above-mentioned adhesive sheet are used by consumers in the market, even if the device is dropped or placed on a heavy object. When unexpected stress is applied to the situation under the circumstances, the collision of flying objects, etc., the above-mentioned adhesive sheet contained in the device can also be used as a reinforcing member to alleviate the stress applied to the device and improve Durability.

此處所揭示之方法例如可良好地用以製造將各種攜帶型設備(可攜式設備)之構成構件作為被黏著體，利用黏著片之圖案局部地覆蓋上述構件之積層體。此處所謂「攜帶」，並不單指能夠攜帶，而係指具有個人(標準成人)能夠相對容易地搬運之程度之攜帶性。又，此處所謂攜帶型設備之例可包括：行動電話、智慧型手機、平板型個人電腦、筆記型個人電腦、各種隨身設備、數位相機、數位攝錄影機、音響設備(攜帶音樂播放器、錄音筆等)、計算機(計算器等)、攜帶型遊戲設備、電子辭典、電子記事本、電子書籍、車載用資訊設備、攜帶型收音機、攜帶型電視、攜帶型印表機、攜帶型掃描儀、攜帶型數據機等攜帶電子設備，此外，亦可包括機械式手錶或懷錶、手電筒、放大鏡等。構成上述攜帶電子設備之構件之例可包括用於液晶顯示器等薄層顯示器或膜型顯示器等之類之圖像顯示裝置之光學膜或顯示面板等。此處所揭示之方法亦可良好地應用於製造將汽車、家電製品等中之各種構件作為被黏著體，利用黏著片之圖案局部地覆蓋該構件之積層體的用途。 [實施例]The method disclosed here can be used, for example, to manufacture a laminated body in which the constituent members of various portable devices (portable devices) are used as adherends, and the above-mentioned members are partially covered by the pattern of the adhesive sheet. The so-called "carrying" here does not only mean being able to be carried, but refers to the portability to the extent that an individual (standard adult) can carry it relatively easily. Also, examples of so-called portable devices here may include: mobile phones, smart phones, tablet personal computers, notebook personal computers, various portable devices, digital cameras, digital video recorders, audio equipment (portable music players) , Voice recorder, etc.), computers (calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, e-books, in-vehicle information equipment, portable radios, portable TVs, portable printers, portable scanners Portable electronic devices such as instrument, portable modem, in addition, can also include mechanical watches or pocket watches, flashlights, magnifying glasses, etc. Examples of the components constituting the above-mentioned portable electronic equipment may include optical films or display panels used in image display devices such as liquid crystal displays or film displays. The method disclosed here can also be well applied to the manufacture of laminates that use various components in automobiles, home appliances, etc. as adherends, and partially cover the components with the pattern of the adhesive sheet. [Example]

以下，說明關於本發明之若干種實施例，但並非意欲將本發明限定於該具體例所示者。再者，以下之說明中之「份」及「%」若無特別說明，則為重量基準。Hereinafter, several embodiments of the present invention will be described, but the present invention is not intended to be limited to those shown in this specific example. In addition, "parts" and "%" in the following descriptions are based on weight unless otherwise specified.

(聚合物A1之製備) 於具備攪拌翼、溫度計、氮氣導入管及冷卻器之反應容器中，加入丙烯酸2-乙基己酯(2EHA)63份、N-乙烯基吡咯啶酮(NVP)15份、甲基丙烯酸甲酯(MMA)9份、丙烯酸2-羥基乙酯(HEA)13份、及作為聚合溶劑之乙酸乙酯200份，於60℃下，於氮氣環境下攪拌2小時後，投入作為熱起始劑之AIBN 0.2份，於60℃下進行6小時反應，而獲得聚合物A1之溶液。該聚合物A1之Mw為110萬。(Preparation of polymer A1) Add 63 parts of 2-ethylhexyl acrylate (2EHA), 15 parts of N-vinylpyrrolidone (NVP), and methyl methacrylate to a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen introduction tube and a cooler. (MMA) 9 parts, 2-hydroxyethyl acrylate (HEA) 13 parts, and 200 parts of ethyl acetate as a polymerization solvent. After stirring for 2 hours at 60°C in a nitrogen atmosphere, they were added as a thermal initiator 0.2 parts of AIBN was reacted at 60°C for 6 hours to obtain a solution of polymer A1. The Mw of the polymer A1 is 1.1 million.

(聚合物A2之製備) 將所使用之單體之組成變更為2EHA/HEA＝95/5(重量比)，除此以外，藉由與聚合物A1之合成相同之方式進行溶液聚合，藉此獲得聚合物A2之溶液。該聚合物A2之Mw為90萬。(Preparation of polymer A2) The composition of the used monomer was changed to 2EHA/HEA=95/5 (weight ratio), except for this, solution polymerization was performed in the same manner as the synthesis of polymer A1, thereby obtaining a solution of polymer A2. The Mw of the polymer A2 is 900,000.

(聚合物A3之製備) 於具備攪拌翼、溫度計、氮氣導入管及冷卻器之反應容器中，加入2EHA 96.2份、HEA 3.8份及作為聚合溶劑之乙酸乙酯150份，於60℃下，於氮氣環境下攪拌2小時後，投入作為熱起始劑之AIBN 0.2份，於60℃下進行6小時反應，而獲得聚合物A3之溶液(固形物成分40%)。該聚合物A3之Mw為54萬。(Preparation of polymer A3) Add 96.2 parts of 2EHA, 3.8 parts of HEA, and 150 parts of ethyl acetate as a polymerization solvent to a reaction vessel equipped with a stirring blade, thermometer, nitrogen introduction tube and cooler, and stir at 60°C for 2 hours in a nitrogen atmosphere. Add 0.2 part of AIBN as a thermal initiator, and react at 60°C for 6 hours to obtain a solution of polymer A3 (solid content 40%). The Mw of the polymer A3 is 540,000.

(聚合物B1之製備) 於具備攪拌翼、溫度計、氮氣導入管及冷卻器之反應容器中，投入MMA 40份、甲基丙烯酸正丁酯(BMA)20份、甲基丙烯酸2-乙基己酯(2EHMA)20份、官能基當量為900 g/mol之含聚有機矽氧烷骨架之甲基丙烯酸酯單體(商品名：X-22-174ASX，信越化學工業股份有限公司製造)9份、官能基當量為4600 g/mol之含聚有機矽氧烷骨架之甲基丙烯酸酯單體(商品名：KF-2012，信越化學工業股份有限公司製造)11份、乙酸乙酯100份、及作為鏈轉移劑之硫甘油0.6份，於70℃下，於氮氣環境下攪拌1小時後，投入作為熱起始劑之AIBN 0.2份，於70℃下進行3小時反應後，進而投入0.1重量份之AIBN，繼而於80℃下反應5小時。以此方式獲得含矽氧烷結構之聚合物B1之溶液。該聚合物B1之Mw為20000。(Preparation of polymer B1) Put 40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), 20 parts of 2-ethylhexyl methacrylate (2EHMA) into a reaction vessel equipped with stirring blades, thermometer, nitrogen introduction tube and cooler. 9 parts of a polyorganosiloxane skeleton-containing methacrylate monomer (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) with a functional group equivalent of 900 g/mol, and a functional group equivalent of 4600 g /mol of 11 parts of methacrylate monomer containing polyorganosiloxane skeleton (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.), 100 parts of ethyl acetate, and thioglycerin as a chain transfer agent 0.6 part, after stirring for 1 hour at 70°C in a nitrogen atmosphere, add 0.2 part of AIBN as a thermal initiator. After reacting at 70°C for 3 hours, add 0.1 part by weight of AIBN, and then at 80°C React for 5 hours. In this way, a solution of polymer B1 containing siloxane structure is obtained. The Mw of the polymer B1 was 20000.

再者，上述各聚合物之重量平均分子量係使用GPC裝置(Tosoh公司製造，HLC-8220GPC)於下述條件下進行測定，藉由聚苯乙烯換算而求出。 ・樣品濃度：0.2 wt%(四氫呋喃(THF)溶液) ・樣品注入量：10 μl ・溶析液：THF・流速：0.6 ml/min ・測定溫度：40℃ ・管柱： 樣品管柱；TSKguardcolumn SuperHZ-H(1根)＋TSKgel SuperHZM-H(2根) 參考管柱；TSKgel SuperH-RC(1根) ・檢測器：示差折射計(RI)In addition, the weight average molecular weight of each polymer mentioned above was measured under the following conditions using a GPC device (Tosoh Corporation make, HLC-8220GPC), and it calculated|required by polystyrene conversion. ・Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution) ・Sample injection volume: 10 μl ・Eluent: THF・Flow rate: 0.6 ml/min ・Measurement temperature: 40°C ・Pipe string: Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2) Reference column; TSKgel SuperH-RC (1 piece) ・Detector: Differential Refractometer (RI)

＜黏著片材之製作＞ (黏著片材D1) 於上述聚合物A1之溶液中，相對於該溶液中所含之聚合物A1之100份，以固形物成分基準計，添加2.5份聚合物B1、2.5份異氰酸酯系交聯劑(商品名：Takenate D110N，三羥甲基丙烷苯二甲基二異氰酸酯，三井化學公司製造)，均勻地混合而製備黏著劑組合物C1。 於未經表面處理之厚度75 μm之PET膜(Toray製造之「Lumirror S10」)之單面直接塗佈黏著劑組合物C1，於110℃下加熱2分鐘而進行乾燥，藉此形成厚度25 μm之黏著劑層，於該黏著劑層之表面(黏著面)貼合剝離襯墊(Mitsubishi Chemical公司製造之MRQ50T100，單面經聚矽氧系剝離劑處理之聚酯膜，厚度50 μm)之剝離處理面而進行保護。以此方式，獲得於包含厚度75 μm之PET膜之基材層之單面具有黏著劑層，且該黏著劑層之表面(黏著面)由剝離襯墊進行保護之形態之黏著片材D1。＜Production of Adhesive Sheet＞ (Adhesive sheet D1) In the above-mentioned solution of polymer A1, with respect to 100 parts of polymer A1 contained in the solution, 2.5 parts of polymer B1 and 2.5 parts of isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals Co., Ltd.) was uniformly mixed to prepare an adhesive composition C1. Coat the adhesive composition C1 directly on one side of a PET film with a thickness of 75 μm (“Lumirror S10” manufactured by Toray) without surface treatment, and heat it at 110°C for 2 minutes to dry, thereby forming a thickness of 25 μm For the adhesive layer, a release liner (MRQ50T100 manufactured by Mitsubishi Chemical Company, a polyester film treated with a silicone release agent on one side, thickness 50 μm) is attached to the surface (adhesive surface) of the adhesive layer Treat the surface for protection. In this way, an adhesive sheet D1 having an adhesive layer on one side of a substrate layer including a PET film with a thickness of 75 μm, and the surface (adhesive surface) of the adhesive layer protected by a release liner was obtained.

(黏著片材D2) 於上述聚合物A1之溶液中，相對於該溶液中所含之聚合物A1之100份，以固形物成分基準計，添加異氰酸酯系交聯劑(商品名：Takenate D110N，三羥甲基丙烷苯二甲基二異氰酸酯，三井化學公司製造)2.5份、光硬化劑(商品名：A-200，聚乙二醇#200二丙烯酸酯，官能基當量154 g/eq，新中村化學工業製造)30份、及光起始劑0.1份，均勻地混合，而製備黏著劑組合物C2。作為光起始劑，使用1-羥基環己基苯己酮(BASF製造之「Irgacure 184」)。 於未經表面處理之厚度75 μm之PET膜(Toray製造之「Lumirror S10」)之單面，使用槽輥直接塗佈黏著劑組合物C2，於130℃下加熱1分鐘而進行乾燥，藉此形成厚度25 μm之黏著劑層。於該黏著劑層之表面(黏著面)貼合剝離襯墊(表面經聚矽氧剝離劑處理之PET膜，厚度25 μm)之剝離處理面而進行保護，於25℃之環境下進行4天老化處理而進行交聯。以此方式，獲得黏著面由剝離襯墊保護之形態之黏著片材D2。(Adhesive sheet D2) In the above-mentioned polymer A1 solution, with respect to 100 parts of the polymer A1 contained in the solution, based on the solid content basis, an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane benzene Dimethyl diisocyanate, manufactured by Mitsui Chemicals Corporation) 2.5 parts, light hardener (trade name: A-200, polyethylene glycol #200 diacrylate, functional group equivalent 154 g/eq, manufactured by Shinnakamura Chemical Industry Co., Ltd.) 30 Part and 0.1 part of the photoinitiator were uniformly mixed to prepare the adhesive composition C2. As the photoinitiator, 1-hydroxycyclohexyl phenhexanone ("Irgacure 184" manufactured by BASF) was used. On one side of a PET film with a thickness of 75 μm (“Lumirror S10” manufactured by Toray) without surface treatment, the adhesive composition C2 was directly coated with a grooved roller, and dried by heating at 130°C for 1 minute. An adhesive layer with a thickness of 25 μm is formed. The surface (adhesive surface) of the adhesive layer is protected by a release liner (PET film with a surface treated with a silicone release agent, thickness 25 μm) for protection, and it is maintained at 25°C for 4 days Cross-linking by aging treatment. In this way, an adhesive sheet D2 with an adhesive surface protected by a release liner is obtained.

(黏著片材D3) 於上述聚合物A2之溶液中，相對於該溶液中所含之聚合物A2之100份，以固形物成分基準計，添加異氰酸酯系交聯劑(商品名：Takenate D110N，三羥甲基丙烷苯二甲基二異氰酸酯，三井化學公司製造)2.5份，均勻地混合而製備黏著劑組合物C3。使用黏著劑組合物C3代替黏著劑組合物C1，除此以外，藉由與黏著片材D1之製作相同之方式獲得黏著面由剝離襯墊保護之形態之黏著片材D3。(Adhesive sheet D3) In the above-mentioned polymer A2 solution, with respect to 100 parts of the polymer A2 contained in the solution, an isocyanate-based crosslinking agent (trade name: Takenate D110N, trimethylolpropane benzene 2.5 parts of dimethyl diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) were uniformly mixed to prepare an adhesive composition C3. The adhesive composition C3 was used instead of the adhesive composition C1, except for this, the adhesive sheet D3 with the adhesive surface protected by the release liner was obtained in the same manner as the production of the adhesive sheet D1.

(黏著片材D4) 不使用聚合物B1，除此以外，藉由與黏著劑組合物C1之製備相同之方式製備黏著劑組合物C4。使用黏著劑組合物C4代替黏著劑組合物C1，除此以外，藉由與黏著片材D1之製作相同之方式，獲得黏著面由剝離襯墊保護之形態之黏著片材D4。(Adhesive sheet D4) Except that the polymer B1 is not used, the adhesive composition C4 is prepared in the same manner as the preparation of the adhesive composition C1. The adhesive composition C4 was used instead of the adhesive composition C1, and other than that, the adhesive sheet D4 with the adhesive surface protected by the release liner was obtained in the same manner as the production of the adhesive sheet D1.

(黏著片材D5) 於上述聚合物A3之溶液中，相對於該溶液中所含之聚合物A3之100份，以固形物成分基準計，添加聚合物B1 2.5份、異氰酸酯系交聯劑(商品名：Coronate L(三羥甲基丙烷/甲苯二異氰酸酯三聚物加成物之75%乙酸乙酯溶液，Tosoh公司製造)3.3份，均勻地混合而製備黏著劑組合物C5。使用黏著劑組合物C5代替黏著劑組合物C1，除此以外，藉由與黏著片材D1之製作相同之方式，獲得黏著面由剝離襯墊保護之形態之黏著片材D5。(Adhesive sheet D5) In the above-mentioned solution of polymer A3, with respect to 100 parts of polymer A3 contained in the solution, 2.5 parts of polymer B1 and isocyanate-based crosslinking agent (trade name: Coronate L( A 75% ethyl acetate solution of trimethylolpropane/toluene diisocyanate trimer adduct, manufactured by Tosoh Corporation) 3.3 parts, uniformly mixed to prepare adhesive composition C5. Adhesive composition C5 was used instead of adhesive In the composition C1, except for this, the adhesive sheet D5 was obtained in a form in which the adhesive surface was protected by the release liner by the same method as the production of the adhesive sheet D1.

＜對聚醯亞胺之黏著力之測定＞ 藉由將厚度12.5 μm之聚醯亞胺膜(Toray-Dupont製造之「Kapton 50EN」)經由雙面黏著帶(日東電工製造之「No.531」)固定於玻璃板，而製作黏著力測定用試片。又，將黏著片材D1～D4及D5裁斷為寬度25 mm之短條狀而製作測定用樣品。 於23℃、50%RH之標準環境下，使2 kg之輥往返1次而使測定用樣品之黏著面壓接至上述試片。將其於上述標準環境下放置30分鐘後，使用拉伸試驗機(Minebea社製造之「TCM-1kNB」)，依據JIS Z0237，於剝離角度180度、拉伸速度300 mm/min之條件下測定剝離強度(初期黏著力)B0 [N/25 mm]。 又，於初期黏著力B0 之測定中，於將測定用樣品壓接至試片後放置於標準環境下，將該放置時間變更為12小時及24小時。關於其他方面，藉由與初期黏著力B0 之測定相同之方式測定室溫12小時後黏著力[N/25 mm]及室溫24小時後黏著力[N/25 mm]。 進而，藉由與初期黏著力B0 之測定相同之方式，將測定用樣品壓接至試片，於常溫(此處約25℃)之螢光燈下保持約4週後，藉由與初期黏著力B0 之測定相同之方式測定剝離強度(4週後黏著力)[N/25 mm]。<Measurement of adhesion to polyimide> By applying a polyimide film with a thickness of 12.5 μm ("Kapton 50EN" manufactured by Toray-Dupont) through a double-sided adhesive tape ("No.531" manufactured by Nitto Denko) ) It is fixed to a glass plate to prepare a test piece for adhesion measurement. In addition, the adhesive sheets D1 to D4 and D5 were cut into short strips with a width of 25 mm to prepare measurement samples. In a standard environment of 23°C and 50%RH, a 2 kg roller was reciprocated once to press the adhesive surface of the measurement sample to the test piece. After placing it in the above-mentioned standard environment for 30 minutes, use a tensile testing machine ("TCM-1kNB" manufactured by Minebea) to measure under the conditions of a peeling angle of 180 degrees and a tensile speed of 300 mm/min in accordance with JIS Z0237 Peel strength (initial adhesion) B 0 [N/25 mm]. Moreover, in the measurement of the initial adhesive force B 0 , after the sample for measurement was crimped to the test piece, it was placed in a standard environment, and the storage time was changed to 12 hours and 24 hours. Regarding other aspects, the adhesive force after 12 hours at room temperature [N/25 mm] and the adhesive force after 24 hours at room temperature [N/25 mm] were measured in the same manner as the initial adhesive force B 0 measurement. Furthermore, the measurement sample was crimped to the test piece by the same method as the measurement of the initial adhesive force B 0 and kept under a fluorescent lamp at room temperature (about 25°C here) for about 4 weeks. The adhesion force B 0 is measured in the same way as the peel strength (adhesion force after 4 weeks) [N/25 mm].

又，藉由與初期黏著力B0 之測定相同之方式將由黏著片材D1、D5所製作之測定用樣品壓接至試片，於上述標準環境下放置30分鐘後，於80℃下加熱5分鐘。進而，於上述標準環境下放置30分鐘後，同樣地於剝離角度180度、拉伸速度300 mm/min之條件下測定剝離強度(加熱後黏著力)[N/25 mm]，結果黏著片材D1為13.94 N/25 mm，黏著片材D5為5.45 N/25 mm。 又，藉由與初期黏著力B0 之測定相同之方式將由黏著片材D2所製作之測定用樣品壓接至試片，於上述標準環境下放置30分鐘後，使用Ushio公司製造之UniField，以成為2000 mJ/cm2 之光量之方式照射主波長約365 nm之紫外線。進而，於上述標準環境下放置30分鐘後，同樣地於剝離角度180度、拉伸速度300 mm/min之條件下測定剝離強度(UV照射後黏著力)[N/25 mm]，結果為19.84 N/25 mm。In addition, the measurement samples made of the adhesive sheets D1 and D5 were crimped to the test piece by the same method as the initial adhesion B 0 measurement, and then placed in the above-mentioned standard environment for 30 minutes, and then heated at 80°C for 5 minute. Furthermore, after being left in the above standard environment for 30 minutes, the peel strength (adhesive force after heating) [N/25 mm] was measured under the same conditions as the peeling angle of 180 degrees and the stretching speed of 300 mm/min, and the result was that the sheet was adhered D1 is 13.94 N/25 mm, and the adhesive sheet D5 is 5.45 N/25 mm. In addition, the measurement sample made from the adhesive sheet D2 was crimped to the test piece by the same method as the initial adhesive force B 0 measurement, and after placing it in the above standard environment for 30 minutes, the UniField manufactured by Ushio was used to Irradiate ultraviolet rays with a dominant wavelength of about 365 nm in a way that becomes 2000 mJ/cm 2 of light. Furthermore, after being left in the above standard environment for 30 minutes, the peel strength (adhesive force after UV irradiation) [N/25 mm] was measured under the same conditions of a peel angle of 180 degrees and a tensile speed of 300 mm/min. The result was 19.84 N/25 mm.

＜積層體之製造＞ (製造例1) 將黏著片材D1裁斷成寬度25 mm、長度100 mm之尺寸，而製備積層體製造用黏著片材。又，作為被黏著體，準備厚度12.5 μm、寬度30 mm、長度120 mm之聚醯亞胺膜(Toray-Dupont公司製造，「Kapton 50EN」)。 將上述被黏著體之中央與上述黏著片材之中央進行位置對準，利用手壓輥將上述黏著片材貼附於上述被黏著體(貼附步驟)。 於將黏著片材貼附於上述被黏著體後且下述局部去除步驟之前，進行切割步驟。於所獲得之黏著片材/被黏著體積層物中之黏著片材之寬度中央，設定自該黏著片材之長度方向之一端呈直線狀延伸至另一端之寬度2 mm、長度100 mm之第二區域，沿該第二區域與其兩側之第一區域之邊界(兩條直線)，自黏著片材面側照射雷射，藉此實施僅將黏著片材D1切斷之切斷加工。上述切斷加工係使用GCC公司製造之雷射切斷裝置「Spirit，Model number SI-30V」，於以下之條件下進行。 速度(Speed)：9.0% 功率(Power)：10.0% DPI：500 PPI：400 於將黏著片材貼附於上述被黏著體後約12小時後，進行局部去除步驟。具體而言，將第二區域之一端自被黏著體剝離，利用拉伸試驗機之夾頭夾住，於剝離角度180度、拉伸速度300 mm/min之條件下沿黏著片材之長度方向進行拉伸，藉此將寬度2 mm之狹縫狀之第二區域自被黏著體剝離去除。 繼而，藉由進行上述加熱(80℃、5分鐘)作為黏著力上升刺激(黏著力上升步驟)，而製作目標之積層體、即利用上述經圖案加工之黏著片材覆蓋上述被黏著體之構成之積層體。表1中，記載有黏著片材D1之室溫12小時後黏著力之值作為製造例1之局部去除步驟時之黏著力，且記載有黏著片材D1之加熱後黏著力之值作為積層體之黏著力。＜Manufacture of laminated body＞ (Manufacturing example 1) The adhesive sheet D1 was cut into a size of 25 mm in width and 100 mm in length to prepare an adhesive sheet for manufacturing a laminate. Also, as the adherend, a polyimide film (manufactured by Toray-Dupont, "Kapton 50EN") with a thickness of 12.5 μm, a width of 30 mm, and a length of 120 mm was prepared. Align the center of the adherend with the center of the adhesive sheet, and attach the adhesive sheet to the adherend with a hand roller (attachment step). After attaching the adhesive sheet to the adherend and before the following partial removal step, a cutting step is performed. In the center of the width of the adhesive sheet in the obtained adhesive sheet/adhesive volume layer, set the first end of the adhesive sheet to extend linearly from one end of the adhesive sheet to the other end with a width of 2 mm and a length of 100 mm. Two areas, along the boundary (two straight lines) between the second area and the first area on both sides, irradiate the laser from the surface of the adhesive sheet, thereby performing a cutting process that only cuts the adhesive sheet D1. The above-mentioned cutting process is performed using the laser cutting device "Spirit, Model number SI-30V" manufactured by GCC Company under the following conditions. Speed: 9.0% Power: 10.0% DPI: 500 PPI: 400 Approximately 12 hours after attaching the adhesive sheet to the above-mentioned adherend, a partial removal step is performed. Specifically, one end of the second area is peeled from the adherend, and clamped by the chuck of a tensile testing machine, along the length of the adhesive sheet under the conditions of a peeling angle of 180 degrees and a tensile speed of 300 mm/min Stretching is carried out, thereby peeling and removing the slit-shaped second area with a width of 2 mm from the adherend. Then, by performing the above heating (80°C, 5 minutes) as an adhesive force increase stimulus (adhesion force increasing step), the target laminated body is produced, that is, the structure of covering the adherend with the patterned adhesive sheet The multilayer body. In Table 1, the value of the adhesive force after 12 hours at room temperature of the adhesive sheet D1 is recorded as the adhesive force during the partial removal step of Manufacturing Example 1, and the value of the adhesive force after heating of the adhesive sheet D1 is recorded as the laminate The adhesion.

(製造例2) 使用黏著片材D2代替黏著片材D1，且於黏著力上升步驟中將施加之刺激自加熱變更為上述UV照射(主波長約365 nm，光量2000 mJ/cm2 )，除上述方面以外，藉由與製造例1相同之程序製造積層體。表1中記載有黏著片材D2之室溫12小時後黏著力之值作為製造例2之局部去除步驟時之黏著力，且記載有黏著片材D2之UV照射後黏著力之值作為積層體之黏著力。(Manufacturing Example 2) Adhesive sheet D2 was used instead of adhesive sheet D1, and the self-heating of the stimulus applied in the step of increasing the adhesive force was changed to the above-mentioned UV irradiation (dominant wavelength of about 365 nm, light intensity of 2000 mJ/cm 2 ) Except for the above points, a laminate was manufactured by the same procedure as in Manufacturing Example 1. Table 1 records the value of the adhesive force of the adhesive sheet D2 after 12 hours at room temperature as the adhesive force during the partial removal step of Manufacturing Example 2, and records the value of the adhesive force of the adhesive sheet D2 after UV irradiation as the laminate The adhesion.

(製造例3、4) 分別使用表1所示之黏著片材，於切割步驟後不進行上述加熱及UV照射之任一者，取而代之，放置於上述標準環境下直至自黏著片材貼附於被黏著體起之經過時間成為24小時為止。關於其他方面，藉由與製造例1相同之程序製造積層體。表1中記載有各黏著片材之室溫12小時後黏著力之值作為製造例3、4之局部去除步驟時之黏著力，且記載有各黏著片材之室溫24小時後黏著力之值作為積層體之黏著力。(Manufacturing examples 3 and 4) Use the adhesive sheets shown in Table 1 respectively. After the cutting step, do not perform any of the above heating and UV irradiation. Instead, place them in the above standard environment until the elapsed time since the adhesive sheet is attached to the adherend It becomes 24 hours. In other respects, the laminate was manufactured by the same procedure as in Manufacturing Example 1. Table 1 records the value of the adhesive force of each adhesive sheet after 12 hours at room temperature as the adhesive force during the partial removal step of Manufacturing Examples 3 and 4, and records the adhesive force of each adhesive sheet after 24 hours at room temperature The value is used as the adhesive force of the laminate.

(製造例5) 於製造例1中，於將黏著片材D1貼附於被黏著體後約11小時後進行上述加熱(80℃、5分鐘)，繼而保持於室溫下直至自將黏著片材D1貼附於被黏著體起之經過時間成為約12小時為止，其後進行局部去除步驟。關於其他方面，藉由與製造例1相同之方式製造積層體。表1中記載有黏著片材D2之加熱後黏著力之值作為製造例5之局部去除步驟時之黏著力。(Manufacturing Example 5) In Production Example 1, the above-mentioned heating (80°C, 5 minutes) was performed about 11 hours after the adhesive sheet D1 was attached to the adherend, and then it was kept at room temperature until the adhesive sheet D1 was attached to the The elapsed time from the adherend is about 12 hours, after which the partial removal step is performed. In other respects, the laminated body was manufactured in the same manner as in Manufacturing Example 1. The value of the adhesive force after heating of the adhesive sheet D2 is described in Table 1 as the adhesive force during the partial removal step of Manufacturing Example 5.

(製造例6、7) 藉由與製造例1相同之方式將黏著片材D1、D2貼附於被黏著體，於維持為上述標準環境之室內，於螢光燈下放置約24小時後，同樣地進行切割步驟，繼而進行局部去除步驟。其後，於上述標準環境之室內保持於螢光燈下，直至自將黏著片材D1、D2貼附於被黏著體起之經過時間成為4週為止，藉此，獲得製造例6、7之積層體。表1中記載有各黏著片材之室溫24小時後黏著力之值作為製造例6、7之局部去除步驟時之黏著力，且記載有各黏著片材之4週後黏著力之值作為積層體之黏著力。(Manufacturing Examples 6, 7) The adhesive sheets D1 and D2 were attached to the adherend in the same manner as in Manufacturing Example 1, and placed in a room maintained in the above-mentioned standard environment under a fluorescent lamp for about 24 hours, and then the same cutting step was performed, and then Perform a partial removal step. Thereafter, the room was kept under a fluorescent lamp in the above-mentioned standard environment until the elapsed time since the adhesive sheets D1 and D2 were attached to the adherend became 4 weeks, thereby obtaining the manufacturing examples 6 and 7 Layered body. Table 1 records the value of the adhesive force of each adhesive sheet after 24 hours at room temperature as the adhesive force during the partial removal step of Manufacturing Examples 6 and 7, and the value of the adhesive force after 4 weeks of each adhesive sheet is recorded as Adhesion of laminated body.

(製造例8) 使用黏著片材D5代替黏著片材D1，除該方面以外，藉由與製造例1相同之程序製造積層體。表1中記載有黏著片材D5之室溫12小時後黏著力之值作為製造例8之局部去除步驟時之黏著力，且記載有黏著片材D5之加熱後黏著力之值作為積層體之黏著力。(Manufacturing Example 8) The adhesive sheet D5 was used instead of the adhesive sheet D1, and except for this point, the laminated body was produced by the same procedure as in Production Example 1. Table 1 records the value of the adhesive force of the adhesive sheet D5 after 12 hours at room temperature as the adhesive force during the partial removal step of Manufacturing Example 8, and records the value of the adhesive force after heating of the adhesive sheet D5 as the laminated body Adhesion.

(狹縫部去除性評價) 於各製造例之局部去除步驟中，於將自被黏著體剝離第二區域時未發現被黏著體發生伸長等變形之情形時評價為「G」(圖案加工性良好)，於發現變形之情形時評價為「P」(圖案加工性不足)。將結果示於表1。 再者，於製造例4、5中，由於未能適當地進行第二區域之剝離，故而未進行以下之耐久性試驗。又，於製造例1～3及6、7、8中，於剝離第二區域時均未發現被黏著體上之糊劑殘留或被黏著體之污染。(Evaluation of slit part removability) In the partial removal step of each manufacturing example, when the second area was peeled from the adherend, no deformation such as elongation was found in the adherend was evaluated as "G" (good pattern processability), and when deformation was found It was evaluated as "P" (insufficient pattern processability). The results are shown in Table 1. Furthermore, in Production Examples 4 and 5, since the peeling of the second region could not be properly performed, the following durability test was not performed. In addition, in manufacturing examples 1 to 3 and 6, 7, and 8, no paste residue on the adherend or contamination of the adherend was found when the second area was peeled off.

(耐久性試驗) 針對藉由製造例1～3及6、7、8所獲得之積層體，使用Yuasa system公司製造之面狀體無負載U字伸縮試驗機「DLDM111LH」及夾具(面狀體無負載U字伸縮試驗夾具)，於伸縮速度30 rpm、彎曲半徑3 mm、伸縮次數100次之條件下進行耐久性試驗。 具體而言，如圖6所示，將樣品60之兩端部x、y利用雙面膠帶(未圖示)固定於上述試驗機之夾板部分61、62後，於上述條件下，重複進行如樣品60自平面之狀態以黏著片材側為內側彎折成彎曲半徑3 mm之U字狀的伸縮。於將樣品60彎折時，藉由夾板之作動使樣品60之兩端部x、y接觸，並且利用另外設置之板部63、64自兩外側將樣品60之其他部分於無負載之條件下夾入。 藉由目視觀察100次伸縮後之樣品之狀態，於黏著片材與被黏著體之間未發現***之情形時評價為「G」(耐久性良好)，於發現***之情形時評價為「P」(耐久性不足)。將結果示於表1。(Durability test) For the laminates obtained by manufacturing examples 1 to 3, 6, 7, and 8, the planar body unloaded U-shaped stretch tester "DLDM111LH" manufactured by Yuasa system company and jigs (the planar body unloaded U-shaped stretch Test fixture), the durability test is carried out under the conditions of a telescopic speed of 30 rpm, a bending radius of 3 mm, and a number of telescopic times of 100 times. Specifically, as shown in FIG. 6, after fixing the two end portions x and y of the sample 60 to the splint portions 61 and 62 of the testing machine with double-sided tape (not shown), under the above conditions, repeat The sample 60 was bent from a flat state with the adhesive sheet side as the inner side into a U-shaped expansion and contraction with a bending radius of 3 mm. When the sample 60 is bent, the two ends x and y of the sample 60 are contacted by the action of the clamping plate, and the other parts of the sample 60 are placed under no-load conditions from the two outer sides using the separately provided plate portions 63 and 64 embed. By visually observing the state of the sample after 100 stretches, it was evaluated as "G" (good durability) when no bulge was found between the adhesive sheet and the adherend, and "P" when bulge was found "(Insufficient durability). The results are shown in Table 1.

[表1]

Figure 108128671-A0304-0001
[Table 1]
Figure 108128671-A0304-0001

如表1所示，黏著力為5 N/25 mm之積層體之製造之製造例1、2、4～7、8中，於黏著力超過2 N/25 mm之前進行了局部去除步驟的製造例1、2、6、7、8中，局部去除步驟中之第二區域之剝離性良好，且製造之積層體顯示出良好之耐久性。於使用具備含有使N-乙烯基環狀醯胺共聚而成之聚合物A1之黏著劑層的黏著片材D1、D2製造積層體之製造例1、2、6、7中，獲得尤其良好之結果。與此相對，製造例3中所獲得之積層體之耐久性較低，製造例4、5中，局部去除步驟中之第二區域之剝離性存在問題。As shown in Table 1, in manufacturing examples 1, 2, 4-7, and 8 for the production of laminates with an adhesive force of 5 N/25 mm, the partial removal step was performed before the adhesive force exceeded 2 N/25 mm. In Examples 1, 2, 6, 7, and 8, the peelability of the second region in the partial removal step was good, and the manufactured laminate showed good durability. Particularly good results were obtained in the production examples 1, 2, 6, and 7 of the laminates using adhesive sheets D1 and D2 with an adhesive layer containing polymer A1 copolymerized with N-vinyl cyclic amide result. On the other hand, the durability of the laminate obtained in Manufacturing Example 3 was low, and in Manufacturing Examples 4 and 5, there was a problem with the peelability of the second region in the partial removal step.

以上，對本發明之具體例進行了詳細說明，但該等僅為例示，並不限定申請專利範圍。申請專利範圍所記載之技術包含將以上所例示之具體例進行各種變化、變更而成者。Above, specific examples of the present invention have been described in detail, but these are only examples and do not limit the scope of patent applications. The technology described in the scope of the patent application includes various changes and modifications to the specific examples illustrated above.

1‧‧‧積層體 10‧‧‧被黏著體 10A‧‧‧表面 20‧‧‧黏著片材 21‧‧‧第一區域 21A‧‧‧黏著片 21B‧‧‧黏著片 22‧‧‧第二區域 50‧‧‧積層體製造裝置 51‧‧‧貼附機構 52‧‧‧切割機構 53‧‧‧剝離機構 60‧‧‧樣品 61‧‧‧夾板部分 62‧‧‧夾板部分 63‧‧‧板部 64‧‧‧板部 202‧‧‧基材層 204‧‧‧黏著劑層 C‧‧‧切斷預定線 L‧‧‧雷射光 S10‧‧‧貼附步驟 S20‧‧‧切割步驟 S30‧‧‧局部去除步驟 x‧‧‧端部 y‧‧‧端部1‧‧‧Layered body 10‧‧‧Adhesive body 10A‧‧‧surface 20‧‧‧Adhesive sheet 21‧‧‧First area 21A‧‧‧Adhesive sheet 21B‧‧‧Adhesive sheet 22‧‧‧Second District 50‧‧‧Laminated body manufacturing equipment 51‧‧‧Attaching Organization 52‧‧‧Cutting mechanism 53‧‧‧Stripping mechanism 60‧‧‧Sample 61‧‧‧Plywood part 62‧‧‧Plywood part 63‧‧‧Board Department 64‧‧‧Board Department 202‧‧‧Substrate layer 204‧‧‧Adhesive layer C‧‧‧Cut off the scheduled line L‧‧‧Laser light S10‧‧‧Attaching steps S20‧‧‧Cutting steps S30‧‧‧Partial removal step x‧‧‧End y‧‧‧end

圖1係表示一實施形態之積層體製造方法之流程圖。 圖2係表示藉由一實施形態之積層體製造方法所製造之積層體之立體圖。 圖3係圖2之III-III線剖視圖。 圖4係說明一實施形態之積層體製造方法之切割步驟之立體圖。 圖5係表示一實施形態之積層體製造方法所使用之積層體製造裝置之概略構成的說明圖。 圖6係表示耐久性試驗之實施方法之說明圖。Fig. 1 is a flowchart showing a method of manufacturing a laminate according to an embodiment. Fig. 2 is a perspective view of a laminated body manufactured by a method of manufacturing a laminated body of an embodiment. Fig. 3 is a sectional view taken along line III-III of Fig. 2; Fig. 4 is a perspective view illustrating a cutting step of a method of manufacturing a laminate of an embodiment. Fig. 5 is an explanatory diagram showing a schematic configuration of a laminated body manufacturing apparatus used in a laminated body manufacturing method of an embodiment. Fig. 6 is an explanatory diagram showing the implementation method of the durability test.

S10‧‧‧貼附步驟 S10‧‧‧Attaching steps

S20‧‧‧切割步驟 S20‧‧‧Cutting steps

S30‧‧‧局部去除步驟 S30‧‧‧Partial removal step

Claims (10)

一種積層體製造方法，該積層體包含被黏著體與局部地覆蓋該被黏著體之黏著片，且上述黏著片對上述被黏著體之黏著力為5N/25mm以上，且該製造方法依序包括：貼附步驟，其係將包含基材層與積層於該基材層之至少上述被黏著體側之面之黏著劑層的黏著片材貼附於上述被黏著體；切割步驟，其係對上述黏著片材中構成上述黏著片之第一區域與不構成上述黏著片之第二區域之邊界實施切斷加工；及局部去除步驟，其係使上述第一區域殘留於上述被黏著體上並且將上述第二區域自上述被黏著體剝離去除；此處，上述黏著劑層包含：聚合物A，其玻璃轉移溫度未達0℃；及聚合物B，其係具有聚有機矽氧烷骨架之單體與(甲基)丙烯酸系單體之共聚物，構成上述聚合物A之單體成分包含N-乙烯基環狀醯胺；且上述N-乙烯基環狀醯胺之使用量，為構成上述聚合物A之單體成分總量之1重量%以上40重量%以下；上述局部去除步驟係於上述黏著片材對上述被黏著體之黏著力超過2N/25mm之前進行；且於上述局部去除步驟之後進行加熱處理而使上述第一區域對上述被黏著體之黏著力為5N/25mm以上。 A method for manufacturing a laminate, the laminate comprising an adherend and an adhesive sheet partially covering the adherend, and the adhesive force of the adhesive sheet to the adherend is 5N/25mm or more, and the manufacturing method sequentially includes ：Attaching step, which is to attach an adhesive sheet comprising a substrate layer and an adhesive layer laminated on at least the side of the adherend of the substrate layer to the adherend; cutting step, which is right In the adhesive sheet, the boundary between the first area constituting the adhesive sheet and the second area not constituting the adhesive sheet is subjected to cutting processing; and a partial removal step in which the first area remains on the adherend and The second region is peeled and removed from the adherend; here, the adhesive layer includes: polymer A, the glass transition temperature of which is less than 0°C; and polymer B, which has a polyorganosiloxane skeleton A copolymer of monomers and (meth)acrylic monomers. The monomer components constituting the above-mentioned polymer A include N-vinyl cyclic amide; and the usage amount of the above-mentioned N-vinyl cyclic amide is the composition The total monomer component of the polymer A is 1% by weight to 40% by weight; the partial removal step is performed before the adhesion of the adhesive sheet to the adherend exceeds 2N/25mm; and the partial removal is performed After the step, heat treatment is performed so that the adhesive force of the first region to the adherend is 5N/25mm or more. 如請求項1之積層體製造方法，其中構成上述聚合物A之單體成分進 而含有含羥基單體。 Such as the method of manufacturing a laminate of claim 1, wherein the monomer components constituting the above polymer A are It contains hydroxyl-containing monomers. 一種積層體製造方法，該積層體包含被黏著體與局部地覆蓋該被黏著體之黏著片，且上述黏著片對上述被黏著體之黏著力為5N/25mm以上，且該製造方法依序包括：貼附步驟，其係將包含基材層與積層於該基材層之至少上述被黏著體側之面之黏著劑層的黏著片材貼附於上述被黏著體；切割步驟，其係對上述黏著片材中構成上述黏著片之第一區域與不構成上述黏著片之第二區域之邊界實施切斷加工；及局部去除步驟，其係使上述第一區域殘留於上述被黏著體上並且將上述第二區域自上述被黏著體剝離去除；此處，黏著劑層包含：聚合物A，其玻璃轉移溫度未達0℃；及聚合物B，其係具有聚有機矽氧烷骨架之單體與(甲基)丙烯酸系單體之共聚物，構成上述聚合物A之單體成分包含N-乙烯基環狀醯胺；且上述N-乙烯基環狀醯胺之使用量，為構成上述聚合物A之單體成分總量之1重量%以上40重量%以下；上述局部去除步驟係於上述黏著片材對上述被黏著體之黏著力超過2N/25mm之前進行；且於上述局部去除步驟之後，於常溫下保管至上述第一區域對上述被黏著體之黏著力成為5N/25mm以上為止。 A method for manufacturing a laminate, the laminate comprising an adherend and an adhesive sheet partially covering the adherend, and the adhesive force of the adhesive sheet to the adherend is 5N/25mm or more, and the manufacturing method sequentially includes ：Attaching step, which is to attach an adhesive sheet comprising a substrate layer and an adhesive layer laminated on at least the side of the adherend of the substrate layer to the adherend; cutting step, which is right In the adhesive sheet, the boundary between the first area constituting the adhesive sheet and the second area not constituting the adhesive sheet is subjected to cutting processing; and a partial removal step in which the first area remains on the adherend and The second region is peeled and removed from the adherend; here, the adhesive layer includes: polymer A, the glass transition temperature of which is less than 0°C; and polymer B, which is a monomer having a polyorganosiloxane skeleton A copolymer with a (meth)acrylic monomer, the monomer component constituting the above-mentioned polymer A includes N-vinyl cyclic amide; and the usage amount of the above-mentioned N-vinyl cyclic amide is to constitute the above 1% by weight to 40% by weight of the total monomer component of polymer A; the above partial removal step is performed before the adhesion of the adhesive sheet to the adherend exceeds 2N/25mm; and the above partial removal step After that, it is stored at room temperature until the adhesion of the first area to the adherend becomes 5N/25mm or more. 如請求項1至3中任一項之積層體製造方法，其中作為上述黏著片 材，使用在貼合於聚醯亞胺後於23℃下經過24小時後之黏著力為2N/25mm以下者。 The method for manufacturing a laminate according to any one of claims 1 to 3, wherein as the adhesive sheet As the material, the adhesive strength of 2N/25mm or less after being attached to polyimide at 23°C for 24 hours. 如請求項1至3中任一項之積層體製造方法，其中上述黏著片材之厚度為30μm以上，且上述基材層之厚度Ts為上述黏著劑層之厚度Ta之2倍以上。 The method for manufacturing a laminate according to any one of claims 1 to 3, wherein the thickness of the adhesive sheet is 30 μm or more, and the thickness Ts of the substrate layer is more than twice the thickness Ta of the adhesive layer. 如請求項1至3中任一項之積層體製造方法，其中上述第二區域係以該第二區域之至少一端到達上述黏著片材之端之方式設定。 The method for manufacturing a laminate according to any one of claims 1 to 3, wherein the second area is set in such a way that at least one end of the second area reaches the end of the adhesive sheet. 如請求項6之積層體製造方法，其中上述第二區域為到達上述黏著片材之端之一端朝向該黏著片材之端變寬之形狀。 The method for manufacturing a laminated body according to claim 6, wherein the second area is a shape in which an end reaching the end of the adhesive sheet widens toward the end of the adhesive sheet. 如請求項1至3中任一項之積層體製造方法，其中上述貼附步驟所使用之上述黏著片材之面積為2500cm2以上，且短邊之長度為50cm以上。 The method for manufacturing a laminate according to any one of claims 1 to 3, wherein the area of the adhesive sheet used in the attaching step is 2500 cm 2 or more, and the length of the short side is 50 cm or more. 如請求項1至3中任一項之積層體製造方法，其中作為上述貼附步驟所使用之上述黏著片材及上述被黏著體，使用包含複數個與上述積層體對應之單元者；且作為上述貼附步驟之後進行之步驟，進而包括將上述黏著片材及上述被黏著體分割成上述單元之分割步驟。 The method for manufacturing a laminate according to any one of claims 1 to 3, wherein the adhesive sheet and the adherend used as the attaching step include a plurality of units corresponding to the laminate; and The step performed after the attaching step further includes a dividing step of dividing the adhesive sheet and the adherend into the units. 一種積層體製造裝置，其係用以實施如請求項1至9中任一項之製造 方法之裝置，且包含：貼附機構，其貼附上述黏著片材；切割機構，其對上述黏著片材實施切斷加工；及剝離機構，其將上述黏著片材之上述第二區域剝離。 A laminated body manufacturing device, which is used to implement the manufacturing of any one of claims 1 to 9 The device of the method and includes: an attaching mechanism that attaches the adhesive sheet; a cutting mechanism that cuts off the adhesive sheet; and a peeling mechanism that peels off the second area of the adhesive sheet.
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